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.     

Empirical Validation of Turbine Engine Exhaust Measurements

The reliability and validity of gas turbine engine exhaust measurements are of concern to all who measure these effluents. In the past, one measure of reliability has been a carbon balance between the fuel used and the C, CO, hydrocarbons, and CO₂ emitted which requires that a F/A ratio be known accurately and that the analyzed sample be representative. In addition to this carbon balance, we have considered the relationships between the concentrations of the several component species. For example, the plot of volume percent of CO₂ versus the volume percent of O₂, both properly corrected to complete combustion, is a straight line. The intercept on the Y-axis (zero oxygen) is a function of the H to C mole ratio in the fuel. This relation has been theoretically established and also established by empirical calculations. For all valid measurements, all points corresponding to CO₂ and O₂ analyses fall on the straight line. In addition, smooth functional relationships exist between other exhaust gas constituents as well, although the form is not a simply derivable linear relationship like that for O₂-CO₂. We have found it useful to employ the following correlations: CO₂ vs. log NO_x, log CO vs. log THC, log CO vs. CO₂, and log THC vs. CO₂- These relationships serve to indicate the probability of reliable data and point out sampling problems and instrument problems such as drift. Subtle changes in engine operation such as opening of the accessory bleed ports in the compressor discharge of the engine can be detected.

The use of a combination of these curves can serve to indicate which measurement is in error. If the O₂-CO₂ relation is linear and the CO-CO₂ relation is smooth, then problems with the total hydrocarbon analyses are indicated when the CO-THC relation is erratic. This would be confirmed by a similar CO₂-THC plot. No useful smooth relationship between smoke density measurements and the other constituents has been found to date. This may indicate poor data, lack of sufficient data, or possibly no correlation.     

Real-Time Measurements of Jet Aircraft Engine Exhaust

Abstract

Particulate-phase exhaust properties from two different types of ground-based jet aircraft engines—high-thrust and turboshaft—were studied with real-time instruments on a portable pallet and additional time-integrated sampling devices. The real-time instruments successfully characterized rapidly changing particulate mass, light absorption, and polycyclic aromatic hydrocarbon (PAH) content. The integrated measurements included particulate-size distributions, PAH, and carbon concentrations for an entire test run (i.e., “run-integrated” measurements). In all cases, the particle-size distributions showed single modes peaking at 20–40nm diameter. Measurements of exhaust from high-thrust F404 engines showed relatively low-light absorption compared with exhaust from a turboshaft engine. Particulate-phase PAH measurements generally varied in phase with both net particulate mass and with light-absorbing particulate concentrations. Unexplained response behavior sometimes occurred with the real-time PAH analyzer, although on average the real-time and integrated PAH methods agreed within the same order of magnitude found in earlier investigations.     

Composition of Exhaust from a Regenerative Turbine System

Particulate and hydrocarbon content of gases in a regenerative gas turbine was analyzed at several points. Particle samples were measured with a condensation nuclei counter, a light scattering single particle counter and an impactor. Hydrocarbon analyses were made using gas chromatography. The effects of operation with JP-4 and No. 2 fuel oil were noted. It was concluded that a regenerative gas turbine will not add appreciably to the burden of air pollution. In fact, particulate contamination levels in the exhaust less than those in the inlet air indicates that the high rotation rate may result in some air cleaning. Low hyd rocarbon contents in the exhaust gas were ascribed to efficient combustion under the operating conditions used in this work. In general, it was concluded that hydrocarbon levels significantly lower than those seen from gasoline or diesel engines could be expected from a well maintained and operated regenerative gas turbine.     

Prospects for Exhaust Control by Engine Modification

In order to assist in assessing potential odor problems arising from chemical manufacturing operations, the odor thresholds of 53 commercially important odorant chemicals have been determined using a standardized and defined procedure. The odor threshold data previously available have shown wide variation reflecting the diversity of procedures and techniques used. Factors that may affect the odor threshold measurement include the mode of presentation of the stimulus to the observer, the influence of extraneous odorants in the presentation system, the type of observer used, the definition of the odor response, the treatment of the data obtained, and the chemical purity of the odorant. The experimental approach used has minimized these variations. The odorants were presented to a trained odor panel in a static air system utilizing a low odor background air as the dilution medium. The odor threshold is defined as the first concentration at which all panel members can recognize the odor. The effect of chemical purity has been determined by measuring the odor threshold of materials representing different modes of manufacture or after purification by gas chromatographic procedures. The threshold concentrations range over six orders of magnitude. Trimethylamine exhibited the lowest threshold (0.00021 ppm volume); methylene chloride was not recognizable below 214 ppm. Of the 53 chemicals, sulfur bearing compounds exhibit low threshold values on the order of parts per billion. Aside from the sulfides, it is not possible to anticipate the odor threshold of a material based on its chemical structure or functionality.     

Subisokinetic Sampling Errors for Aircraft Turbine Engine Smoke Probes

The years 2012 and beyond seem likely to record major changes in energy use and power generation. The Japanese tsunami has resulted in large countries either scaling back or abolishing the future use of nuclear energy. The discovery of what seems like vast amounts of economically deliverable natural gas has many forecasting a rapid switch from coal- to gas-fired generating plants. On the other hand, environmentalists have strong objections to the production of natural gas and of petroleum by hydraulic fracturing from shale, or by extraction of heavy oil. They believe that global warming from the use of fossil fuels is now established beyond question. There has been rapid progress in the development of alternative energy supplies, particularly from on-shore and off-shore wind. Progress toward a viable future energy mix has been slowed by a U.S. energy policy that seems to many to be driven by politics. The author will review the history of power and energy to put all of the above in context and will look at possible future developments. He will propose what he believes to be an idealized energy policy that could result in an optimum system that would be arrived at democratically.

Implications The combustion energy sector is believed to be a dominant component of environmental pollution. A multitude of technologies support this sector and many have the potential to replace elements of this sector with low-polluting processes. This review covers a selection of energy production technologies that are important for the future. A historical perspective is provided to advance the general knowledge about these technologies as options for the world's increasing demand for energy. In addition, a decarbonization policy option for an energy fee is proposed as an alternative to carbon taxation or cap-and-trade approaches.     

Evaluation of the Iron-o-Phenanthroline Procedure For Determining S02 in Turbine Exhaust Gases

Several wet chemical methods have been used or suggested for the determination of SO₂ concentrations in air pollution work. These include the iron-O-phenanthroline procedure reported by Stephens and Lindstrom, the Scaringelli-modified West-Gaeke method and the Schulze method. This paper describes a laboratory study to evaluate the usefulness of the iron-o-phenanthroline procedure and is directed to individuals concerned with the analysis of gases from the exhaust of gas turbine engines and other combustion processes, including stationary power plants. The variables considered were: range of usefulness in terms of concentration of SO₂, efficiency of collection, effect of contaminants, specifically oxides of nitrogen, olefin and aldehyde and effect of storage prior to spectrophctometric measurement. The Stephens-Lindstrom method was found to be suitable for measuring higher levels of SO₂ concentrations. It can accurately measure amounts totalling 6000 µl of SO₂ and above whereas the other mentioned methods are generally used for lower levels. Collection efficiency was satisfactory. Contaminants, particularly oxides of nitrogen, are a problem only at low levels of SO₂. NO₂ interference may be eliminated by absorption of the NO₂ on Ultraport S impregnated with ANEDA/H₂SO₄ solution. Temperature control during SO₂ addition is necessary. Storage of exposed reagents prior to measurement produce only small errors if stored at 0°C or at room temperature.     

Standard Reference Gases and Analytical Procedures for Use in Gas Turbine Exhaust Measurements

This paper is directed to people who are involved in the measurement of gas turbine exhaust emissions and as a consequence in the establishment of standard reference gases and attendant analytical procedures.

Several problems exist in connection with the establishment of these standards:

A number of standard reference gases have been developed by the National Bureau of Standards for use in the automotive industry which are also suitable for gas turbine exhaust measurements. However, there is a need for additional standard reference materials such as NO in nitrogen, intermediate levels of CO₂ in air, and higher concentrations of CO in nitrogen and propane in air.

There is difficulty in maintaining certain reference materials with confidence in assay, particularly due to instability in the cylinder.

Instrumental operational problems with flame ionization detector type units exist. Of particular importance is the difference in response per carbon atom in different organic molecules and the difference in response of a test sample as a function of the oxygen content of the sample.

Instrumental method problems such as converter efficiency in chemiluminescence units measuring NO₂ and calibration techniques involving CO to CH₄ conversion, also must be considered.

A number of problems occur in the use of wet chemical reference methods such as the phenoldisulfonic acid method for the determination of NO_x. These include both efficiency of collection, conversion of NO to NO₂, and subsequent analysis.

This paper considers the development of standards for the measurement of NO_x, CO, CO₂, total hydrocarbons, and O₂ and reviews the state-of-the-art with respect to these problems and their resolution.     

The Influence of Improved Mixture Quality on Engine Exhaust Em issions ana Performance

A large, steam-heated, fuel vaporization tank was utilized as a carburetor in multicylinder engine testing at steady-state operating conditions. In comparison to normal carburetion, the tank provided improved air-fuel mixture quality, i.e., completely vaporized fuel, thoroughly mixed with air, and at elevated temperatures. Although not a practical piece of engine hardware, the tank provided a means of determining the extent of gains to be made with improved mixture quality. Improved mixture quality produced slight reductions in rich mixture hydrocarbon and carbon monoxide concentrations but did not reduce the minimum emissions of these two exhaust contaminants. Minimum fuel consumption was similarly unaffected by improved mixture quality. The most important benefit of improved mixture quality was derived from improved geometric and cyclic fuel distribution—a substantial extension of the misfire lean limit. The significance of lean limit operation and its relationship to reduced exhaust contaminants is discussed in detail.     

Evaluation of Saltzman and Phenoldisulfonic Acid Methods for Determining NOx in Engine Exhaust Gases

The two methods normally used for the analysis of NO_x are the Saltzman and the phenoldisulfonic acid technique. This paper describes an evaluation of these wet chemical methods to determine their practical application to engine exhaust gas analysis. Parameters considered for the Saltzman method included bubbler collection efficiency, NO to NO₂ conversion efficiency, masking effect of other contaminants usually present in exhaust gases and the time-temperature effect of these contaminants on stored developed solutions. Collection efficiency and the effects of contaminants were also considered for the phenoldisulfonic acid method. Test results indicated satisfactory collection and conversion efficiencies for the Saltzman method, but contaminants seriously affected the measurement accuracy particularly if the developed solution was stored for a number of hours at room temperature before analysis. Storage at 32°F minimized effect. The standard procedure for the phenoldisulfonic acid method gave good results, but the process was found to be too time consuming for routine analysis and measured only total NO_x.     

Techniques and Procedures for the Measurement of Aircraft Gas Turbine Engine Emissions

In 1968 the Society of Automotive Engineers formed the Committee on Aircraft Exhaust Emissions Measurement (E-31) whose charge was the development of acceptable standards of measurement for the characterization of aircraft engine exhaust. This committee’s efforts have resulted in the issuance of two Aerospace Recommended Practices, ARP 1179 “Aircraft Gas Turbine Exhaust Smoke Measurement” and ARP 1256 “Procedure for the Continuous Sampling and Measurement of Gaseous Emissions from Aircraft Turbine Engines.” These Recommended Practices have in large part been adopted by the Environmental Protection Agency and promulgated in Federal Register Volume 38, Number 136, Tuesday, July 17, 1973.

For the past three years Pratt & Whitney Aircraft has been measuring emissions from aircraft gas turbine engines using on-line instrumentation systems designed both in accordance with these Aerospace Recommended Practices and in response to the operational needs of a large experimental engineering test facility. In addition to a discussion of these systems this paper describes the experience derived from continuous testing programs in support of this test facility with consideration being given to the specific problems of sampling, sample handling, system accuracy, and data recording and reduction. Comment is made as to the practical limitations of the recommended methods and procedures as applied to emission control technology programs and suggestions are presented for improving the measurement technology.     

Control of Particulate Emissions from Turbine Engine Test Cells by Cooling Water Injection

Abstract

This paper presents an experimental study of calcium bisulfite oxidation, a key step in the wet limestone-gypsum flue gas desulfurization (FGD) process, in the presence of catalysts (e.g., cobalt ions and a mixture of ferrous and cobalt ions). A fundamental approach is followed, by reproducing a simplified synthetic FGD liquor in which both catalyst ions, alone or mixed together, are present. A laboratory-scale apparatus is used, in which sulfurous solution is contacted with a gas phase at a fixed oxygen partial pressure (21.3 kPa) and at different temperature levels (25, 45, and 55 °C). The experimental results are analyzed using the theory of gas-liquid mass transfer with chemical reaction, showing that the slow reaction regime is explored and the transition from the kinetic to the diffusional subregime is identified. The experimental results are compared with those obtained in the presence of other catalytic species (manganese and ferrous ions), showing that cobalt is effective in catalyzing the oxidation of calcium bisulfite to sulfate, but to a minor extent with respect to iron and manganese.     

Use of Diisobutylene Fuel in a Single Cylinder Engine: Effects of Equivalence Ratio on Exhaust Composition

This study describes the variations in the chemical composition of the exhaust at various equivalence ratios (air-fuel ratios) when pure diisobutylene (2,4,4-trimethyl-l-pentene) is used as a fuel in a Labeco single cylinder engine. The exhaust hydrocarbon products from diisobutylene consist of two types: those which decrease as the equivalence ratio is increased: methane, ethylene, acetylene, diisobutylene; and those which exhibit a maximum near an equivalence ratio of 1, then decrease: propylene, propadiene, isobutyl-ene, ethane, 2-methyl-l-butene. The combustion of diisobutylene produces two olefins in low yield which are not observed in the combustion of isooctane fuel. These are 2,4-dimethyl-l,3-pentadiene, probably derived from pyrolytic decomposition of C₇-alkyl radicals, and 3,5,5-trimethyl-2-hexene, probably arising from methyl radical addition to the alpha carbon of the parent fuel molecule. Comparison of the photochemical reactivity of dissobutylene exhaust to that of isooctane at a fuel-lean condition, indicates that diisobutylene, surprisingly, exhibits lower total photochemical reactivity.     

Noncatalytic Auto Exhaust Combustor

Present methods for the determination of carbon monoxide are discussed including indicator tubes, the iodine pentoxide reaction and measurement by gas chromatography. In the gas chromatographic method an air sample is separated on a gas-solid chromatogra-phic column and the separated CO is converted to methane by hydrogenation at elevated temperature. The separated CO, in the form of methane, is passed into a hydrogen flame detector and measured. The conversion from CO to methane allows the use of a sensitive ionization detector in place of the thermal conductivity cell which is insufficiently sensitive for the measurement of trace amounts of CO. The optimum operating conditions are discussed. It is possible to determine one ppm CO in air. The iodine pentoxide reaction with CO has been combined with electrometric measurement. The iodine liberated is passed into a Ditte cell and the current generated is measured by an electrometerrecorder combination. This method is continuously direct reading with a permanent record. It is suitable for the continuous routine analysis of one ppm CO.     

Benzene in Auto Exhaust

The gas phase thermal decomposition rates of the C₁ and C₂-substituted peroxyacyl nitrates (RC(O)OONO₂), PAN (R = CH₃), PPN (R = C₂H₅) and vinyl-PAN (R = CH₂ = CH-) have been measured at ambient temperature (288 - 299 K) and 1 atm. of air. Our results for PAN (k = A exp (-E_a/RT), log₁₀ (A, s^-1) = 16.2 ± 1.6, E_a = 26.9 ± 2.1 kcal / mol, k₂₉₈ = 3.0 × 10^?4S^?1) are consistent with literature data. Thermal decomposition rates for PPN and vinyl-PAN are similar to that for PAN, with k₂₉₈ = 3.0 × 10^?4S^?1 for PAN, 3.4 × 10^?4S^?1 for PPN and 3.0 × 10^?4S^?1 for vinyl-PAN. Implications for the atmospheric persistence of PPN and vinyl-PAN as compared to that of PAN are briefly discussed.     

Automobile Exhaust Control Devices

Irritant gases in concentrations that occur in polluted atmospheres might play a role in the degranulation and histamine release processes of mast cells in lung tissue. To test this hypothesis, young rats weighing 140-150 g were exposed to 1 ppm nitrogen dioxide for 2 hr. One group was killed immediately, and another group 24-27 hr after exposure. A third group was exposed to 0.5 ppm nitrogen dioxide for 4 hr and killed immediately. Animals serving as controls were placed for 1 hr into the exposure chamber ventilated with ambient air. Standard histological preparations were made after Carnoy’s fixative and subsequent staining with toluidine blue. The mast cells of the control animals appeared relatively intact with no evidence of disorientation. The cells of the animals exposed to NO2 and sacrificed immediately revealed rupture and loss of cytoplasmic granules with some disorientation. These changes were observed in the pleura, bronchi, and surrounding tissue with the effects more marked in the mediastinum. The mast cells of exposed animals sacrificed about 24-27 hr after discontinuing the exposure showed in some cases a combination of ruptured and intact cells with a predominance of the latter, and in other cases could not be differentiated from the controls. These findings indicate that 24 hr or more are required to reverse the acute effects of NO2 inhalation. The toxicological implications will be discussed. The release of granular substances in the lung tissue when NO2 is inhaled signifies the onset of an acute inflammation.     

California Vehicle Exhaust Control

The purpose of this paper is to relate California’s experience with vehicle exhaust controls for three model years and to discuss future possibilities for improving the continued effectiveness of these controls. Tests of exhaust controls on 1966 and subsequent model cars in public use indicate a reduction in hydrocarbons of about 60% for the vehicle life of 100,000 miles compared to uncontrolled cars. However, emission levels and emission deterioration rates in public use are higher than those reported from proving ground tests. Significant percentages of new cars are delivered from the factory maladjusted which has a significant effect on emissions. These maladjustments are worsened by automotive service personnel.     

Measurement of Automobile Exhaust GAS Hydrocarbons

While snowflakes fell and Christmas carols heralded the imminent holiday, over 3000 delegates to the Third National Conference on Air Pollution were told to “Control Now for Clean Air.”

They were told this in many ways by many people—by the Vice President of the United States; by the Secretary of the Department of Health, Education, and Welfare who summoned the Conference; and by senators, congressmen, governors, and mayors.

Then eight panel sessions convened to discuss and to determine how to control now for clean air. Speakers from every section of American life addressed themselves to this subject; when they were finished, the eight session chairmen summarized what had been said, what had been, learned. These summaries appear on the following pages.     

Nature of Odor Components in Diesel Exhaust

Offensive exhaust odors are characteristic of diesel engines. One problem in control and reduction of odor is lack of understanding of odorant sources and mode of formation. The solution of this problem depends on identification of the odorants so that study of their formation and control can be undertaken. A human panel performed odor assessments in studying raw and modified diesel exhaust and synthetic blends representing portions of diesel exhaust. Their assessments were used in determining odorant identity and quantitative contribution to exhaust odor. Low molecular weight aldehydes appear to contribute little to diesel odors. The sulfur and nitrogen oxides have been examined as odorants but of these apparently only nitrogen dioxide is a potential odor contributor.