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.     

Desulfurization of Flue Gases in A Fluidized Bed of Modified Limestone

This publication concerns the dry removal of SO₂ from gases using limestone absorbents. It reports bench-scale experiments made with commercial samples of powdered limestone (CaCO₃) activated by addition of a cheap substance, namely CaCl₂. The absorption was carried out in a fluidized bed traversed by the flue gases, between 600° and 900° C. The degree and rate of transformation of CaCO₃ to CaSO₄ in the presence of SO₂ and air have been compared for unmodified and modified absorbents. Initial rates of reaction, and the variation of the rate of absorption with time have been measured. The influence of the SO₂ content of the gas has been assessed. At 700° C, the maximum degree of transformation of activated limestone to sulfate exceeds 90%, whereas untreated CaCO₃ transforms only to 16–20%. At the same temperature, more than 90% of SO₂ contained In a gas carrying 0.35% SO₂ is removed. Because of the much smaller quantity of solid absorbent required, dry absorption processes based on the modified absorbents might get renewed interest. The modified absorbents might also be used for in situ absorption in fluidized bed combustion, in which the temperatures are in the range studied in the present paper.     

Reactive and Unreactive Hydrocarbon Emissions from Gas Turbine Engines

Hydrocarbon emissions from gas turbine engines can be divided into unreactive and reactive components. The unreactive component consists of paraffins which do not take part in smog producing reactions with NO_x. The reactive portion includes olefins, aro-matics and oxygenated derivatives of hydrocarbons which take part in smog producing reactions with NO_x. Odor is attributed normally to the aromatics and oxygenates.

Previous work led to the development of a high temperature subtractive analyzer (APCA 22, 696 (1972) which separates hydrocarbon emissions into a) paraffins and b) aromatics, olefins, and oxygenates. Liquid chromatographic techniques have also been used to separate the hydrocarbons into a) aliphatics, b) aromatics, and c) oxygenates. These aliphatics include olefins.

In this work, engine emissions have been analyzed by these two techniques as a function of engine type, engine thrust (power) and fuel type. Specific engines tested were JT4, JT3D and JT9D. Fuels studied were JP5, and Jet A fuel. Power settings ranged from sub idle to high power. Results using the high temperature subtractive analyzer indicate that the % unreactive hydrocarbons ranges from 30 % at idle to near zero at high power for these engine types and fuels. In general, the higher the total hydrocarbon level, the higher the % unreactive hydrocarbons. Total hydrocarbons decrease sharply with increase in thrust. The emissions from different types of engines at various power settings were collected on an adsorbent Chromosorb 102 and the adsorbate analyzed by liquid chromatographic techniques at A. D. Little, Inc. These results showed similar trends from low power to high power. The oxygenate fraction increased and aliphatic portion decreased. However, the data for this portion of the work were very limited and no firm conclusions can be drawn.     

Development of a 24-Hour Method for Analysis of SO2 and CO2 from Electric Utility Units Equipped with Flue Gas Desulfurization Scrubbers

A procedure was developed for the 24-h determination of SO₂ and CO₂ in effluent gas from fossil fuel combustion sources. Laboratory experiments were conducted to test absorption of SO₂ in hydrogen peroxide solution and absorption of CO₂ by sodium hydroxide on an inert substrate at expected ambient temperatures of 15 to 45°C. Isopropyl alcohol cannot be used to trap sulfuric acid and particulates because it permeates the sampling train and prevents complete absorption of CO₂. Elemental analysis of stack particulates revealed that at least 31 elements were present. Iron and other elements interfered with SO₂ analysis. These particulates were completely removed by a heated borosilicate glass filter. Both laboratory and field experiments showed that molecular sieves are a promising alternative for CO₂ absorption. Statistical evaluation of data collected at three units equipped with flue gas desulfurization scrubbers proved that the new procedure is accurate and precise.     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Odor Threshold Measurement by Dynamic Olfactometry: Significant Operational Variables

Abstract

Combustion flue gases of three different industrial boilers firing miscellaneous fuels were monitored for a twoweek period. Nitric oxide (NO), sulfur dioxide (SO₂), carbon monoxide (CO), carbon dioxide (CO₂), and total hydrocarbons (CxHy) were continuously measured using single-component gas analyzers in parallel with a lowresolution Fourier Transform Infrared (FTIR) gas analyzer. Hydrogen chloride (HCl) was measured continuously using the FTIR analyzer and semi-continuously using a traditional liquid-absorption technique. Nitrous oxide (N₂O), nitrogen dioxide (NO₂), and water vapor (H₂O) were continuously measured using the FTIR analyzer only. Laboratory tests were conducted prior to the field measurements to assess the detection limits of the different measurement methods for each gas component. No significant differences were found between the results of the low-resolution FTIR analyzer and the single-component analyzers or the liquid absorption method.     

Concentrations of C2–C5 hydrocarbons in atmospheric air at Deonar,Bombay, in relation to possible sources

Atmospheric C₂–C₅ hydrocarbons were determined at Deonar, an industrial suburb north of Bombay, India, during 1985. Samples were pre-concentrated on silica gel at −78°C and subsequently desorbed on to a gaschromatographic column for separation and flame ionization detection. The seasonal pattern of the monthly geometric mean hydrocarbon concentrations are used to show that refinery emissions in addition to auto exhaust are a major source of hydrocarbons at Deonar.     

Atmospheric oxidation of elemental mercury by ozone in the aqueous phase

The aqueous phase oxidation of elemental mercury by ozone has been investigated in the laboratory using a quartz glass reactor with gas phase concentrations of 400–1800ng m⁻³ and 70–200 ppb for Hg(0) and O₃, respectively. The absorption of Hg in the water phase was increased by three orders of magnitude with O₃ present. If the oxidation were to proceed with the same speed in liquid water in contact with the atmosphere,conversion rales of 1–4% h⁻¹ would be implied. Experiments using ambient urban air with 2–6 ng Hg m⁻³ confirm the process at elevated O₃ concentrations. At ambient O₃ concentrations competitive reactions become important, e.g. O₃ consumption by SO₂, hydrocarbons etc., and even some reduction of Hg²⁺ could occur. The atmospheric oxidation of Hg(0) by O₃ in water is thus considered important at high O₃ levels in regionally polluted or remote areas.     

Analysis for Exhaust Gas Hydrocarbons—Nondispersive Infrared Versus Flame-lonizaticn

An investigation has been made of the suitability of a nondispersive infrared analyzer and two flame-ionization analyzers for measuring the total hydrocarbon concentrations of automobile exhaust gas. The investigation consisted of measuring relative responses of various hydrocarbons, checking for possible exhaust gas interferences and finally comparing exhaust hydrocarbon concentrations indicated by the flame-ionization analyzer to those indicated by the infrared analyzer. The infrared analyzer has high relative responses for parraffins and low responses for olefins, acetylenes, and aromatics. Also, the infrared indicated hydrocarbon concentrations must be corrected for exhaust water vapor interference. When the flameionization analyzers are operated at conditions that result in approximately uniform response to hydrocarbons and low oxygen interference, the exhaust hydrocarbon concentrations indicated by either flameionization analyzer are better approximations of the total hydrocarbon concentration than those indicated by the infrared analyzer.     

Ammonia concentrations and modeling of inorganic particulate matter in the vicinity of an egg production facility in Southeastern USA

Ammonia (NH₃) is an important base gas and can react with acidic species to form atmospheric aerosols. Due to the rapid growth of poultry and swine production in the North Carolina Coastal Plain, atmospheric NH₃ concentrations across the region have subsequently increased. Ammonia concentrations and inorganic particulate matter (PM) at four ambient stations in the vicinity of an egg production facility were measured for 1 year using PM_2.5 speciation samplers with honeycomb denuders and ion chromatography (IC). Meanwhile, concentrations of NH₃ and inorganic PM in one of the egg production houses were also simultaneously measured using a gas analyzer for NH₃ and the filter pack plus IC method for inorganic PM. An equilibrium model-ISORROPIA II was applied to predict the behavior of inorganic aerosols in response to precursor gas concentrations and environmental parameters. Average ambient NH₃ concentrations varied from 10.0 to 27.0 μg/m³, and they were negatively correlated with the distances from the ambient location to the nearest egg production house exhausts. Ambient NH₃ concentrations were higher in warm seasons than in cold seasons. Measured NH₃ concentrations agreed well with ISORROPIA II model predictions at all sampling stations. For the ambient stations, there was a good agreement in particle phase NH₄ ⁺ between the model simulation and observations. For the in-house station, the model simulation was applied to correct the overestimation of particle phase NH₄ ⁺ due to gas phase NH₃ breaking through the denuders. Changes in SO₄ ^2?, NO₃ ^?, and Cl^? yield proportional changes in inorganic PM mass. Due to the abundance of NH₃ gas in the vicinity area of the monitored farm, changes in NH₃ concentrations had a small effect on inorganic PM mass. Aerosol equilibrium modeling may be used to assess the influence of precursor gas concentrations on inorganic PM formation when the measurements for some species are unavailable.     

Detailed chemical modelling of a flameless combustion turbine for pollution prevention

Flameless combustion has been acknowledged as one of the most interesting combustion technologies to meet both the targets of high process efficiency and low pollutant emissions. The present investigation is concerned with the application of the flameless combustion mode to an adiabatic combustor, typically used in gas turbine engines. Detailed chemical kinetics calculations, by means of a specific zero dimensional loop reactor model, have been performed to analyse its chemical aspects. The main objective of this study is to provide a fundamental understanding of the physical and chemical processes that occur during combustion in high-temperature air or exhaust gases with a low content of oxygen. The detailed chemistry approach, based on the comprehensive (GRI_MECH3.0 mechanism) oxidation kinetics of methane, is used. Simulation results clearly illustrate that even at high operating temperatures and pressures, NO_x emissions could be reduced by flameless combustion to very low levels. The flameless oxidation then appears as a promising technique for industrial gas turbine combustor applications.     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Determination of Source Contributions to Ambient PM2.5 in Kaohsiung,Taiwan, Using a Receptor Model

ABSTRACT

Ambient particulates of PM_2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM_2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM_2.5.

The mean concentration of ambient PM_2.5 was 42.6953.68 μj.g/m³ for the sampling period. The abundant species in ambient PM_2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO₄ ^2- (12.8-15.1%), NO₃ ^- (8.110.3%), NH₄+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM_2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO₄ ^2- and NO₃ ^-), and outdoor burning of agriculture wastes (13-17%).     

Product Guide/1970

Abstract

In Mexico City, the use and composition of fuels determine that carbon monoxide (CO) comes mostly from mobile sources, and sulfur dioxide (SO₂) from fixed and mobile sources. By simultaneously measuring hydrocarbons (HC), CO, and SO₂ in the atmosphere of Mexico City, the relative amounts coming from different sources can be estimated. Assuming that some HC are emitted proportionally to CO emissions, we can establish that [HC]₁= m1? [CO], where the proportionality constant ml corresponds to the ratio of emissions factor for HC and CO in mobile sources. Similarly for fuels containing sulfur, it can be assumed that [HC]₂ = m2 ? [SO₂]. In this way, the total HC are [HC]_total=[HC]₀+ ml ? [CO]+ m2 ? [SO₂], where [HC]₀ corresponds mainly to other sources like solvent evaporation, gas consumption, and natural emissions. In this way, it can be estimated that in Mexico City 75% of average HC comes from mobile sources, 5% from sulfur-related sources, and 19% from natural sources and solvent evaporation. Compared with the HC/CO ratio measured in the exhaust pipe of vehicles, we estimated that 70% of HC emitted from mobile sources are evaporative losses, and only 30% come through the exhaust system.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Emissions profile from new and in-use handheld, 2-stroke engines

The objective of this study was to characterize exhaust emissions from a series of handheld, 2-stroke small engines. A total of 23 new and used engines from model years 1981–2003 were studied; these engines spanned three phases of emission control (pre-control, phase-1, phase-2). Measured emissions included carbon monoxide (CO), carbon dioxide (CO₂), nitrogen oxides (NO_x), hydrocarbons (HC), fine particulate matter (PM_2.5), and sulfur dioxide (SO₂). Emissions reductions in CO (78%) and HC (52%) were significant between pre-control and phase-2 engines. These reductions can be attributed to improvements in engine design, reduced scavenging losses, and implementation of catalytic exhaust control. Total hydrocarbon emissions were strongly correlated with fuel consumption rates, indicating varying degrees of scavenging losses during the intake/exhaust stroke. The use of a reformulated gasoline containing 10% ethanol resulted in a 15% decrease in HC and a 29% decrease in CO emissions, on average. Increasing oil content of 2-stroke engine fuels results in a substantial increase of PM_2.5 emissions as well as smaller increases in HC and CO emissions. Results from this study enhance existing emission inventories and appear to validate predicted improvements to ambient air quality through implementation of new phase-2 handheld emission standards.     

Health Risks of Short-term S02 Exposure to Exercising Asthmatics

A method is described for quantifying health risks to asthmatics briefly exposed to elevated levels of SO₂. By combining symptomologlcal and physiological measurements, we have developed a dose-response surface that relates both severity and incidence of response to ambient air quality levels. The complete model to assess potentially avoidable risks includes power plant emission data; ambient SO₂ background levels; demographic and activity patterns of asthmatics, the identified population at risk; and the dose-response surface. The estimated annual risk to persons experiencing an SO₂-lnduced response due to a nearby power plant is quite small (response rates under 3 percent). Uncertainties due to modeling errors, variations in activity patterns, demographics and physiological response are discussed.     

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.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

A new sampling device is described for the simultaneous collection of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min⁻¹ the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH₃, HNO₃, HCL and SO₂ are in the order of 0.1–0.5 μm⁻³. For H₂O₂ the detection limit is 0.01 μm⁻³. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.