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1.
ABSTRACT

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr2O3) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300–14,700 mg/m3 and 240–400 ° C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained.

Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results.

In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr2O3 catalyst.  相似文献   

2.
ABSTRACT

Dalton's law of partial pressures and the hypothesis that water vapor equilibrium in a canister is identical to that established above liquid water are used to predict the variation of the percent relative humidity (%RH) of air released from canisters used in ambient air sampling, typically 6-L canisters pressurized with 18 L of air. When (and if) the water vapor partial pressure in a canister exceeds its saturation vapor pressure, water vapor condensation begins and the condensation rate equals the sampling rate of water vapor into the canister. Under constant temperature conditions, the air subsequently released from the canister is less humid than the original sample, following the relationship %RH = 100% (6 L/Vs) for Vs> Vr, where Vs is the residual air volume (referenced to atmospheric pressure), and Vr is shown to depend on the %RH of the ambient air sample. Vr is the residual air volume at which water is completely removed (except for adsorbed water vapor) from the canister wall. For Vs < Vr, the predicted %RH is constant and equal to its value at Vr. Experimental values agree reasonably well with predictions at both high (90%) and low (34%) RH. However, experimental values are often slightly displaced (usually towards lower values of %RH) for mid-range %RH (61%) and variations in %RH near Vr change from canister to canister.  相似文献   

3.
Abstract

The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 μm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.  相似文献   

4.
Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10-5 based on average values.  相似文献   

5.
Abstract

A badge-type passive monitor was used to evaluate the effectiveness of four ozone trapping reagents for measuring O3 concentrations in the air. These were sodium nitrite (NaNO2), 3-methyl-2-benzothiazolinone acetone azine (MBTH), p-acetamidophenol (p-ATP), and indigo carmine. Experiments in an exposure chamber showed that only NaNO2 and MBTH monitors gave sensitive and linear responses over realistic ranges of O3 concentrations. When tested in ambient air, NaNO2 and MBTH monitors with a single-layer diffusion barrier overestimated O3 concentrations by a significant amount. This was largely canceled out in the NaNO2 monitor by using a multi-layered diffusion barrier to combat wind turbulence effects. However it had almost no effect on the MBTH monitor, and it was found that NO2 was a source of serious interference. We concluded that using the NaNO2 monitor with an effective diffusion barrier can measure O3 in ambient air with an accuracy of ±16%.  相似文献   

6.
Abstract

Based on exhaust gas analyses from the combustion of five different types of gasoline in a passenger car operated on a chassis dynamometer, box model simulations of the irradiation of exhaust/NOx /air mixtures using an established chemical mechanism for a standardized photo-smog scenario were performed. The fuel matrix used covered wide fractional ranges for paraffinic, olefinic, and aromatic hydrocarbons. Two fuels also contained methyl tertiary butyl ether (MTBE). The different O3 profiles calculated for each run were compared and interpreted. The O3 levels obtained were strongly influenced by the exhaust gas concentrations of aromatic and olefinic hydro-carbons. The higher exhaust content of these compounds caused higher O3 production in the smog system investigated. The conclusion of the present study is that the composition of gasoline cannot be taken directly for the estimation of the emissions’ O3 creation potential from its combustion. Variation of the dilution in the different calculations showed evidence for an additional influence of transport effects. Accordingly, further detailed exhaust gas analyses followed by more complex modeling studies are necessary for a proper characterization of the relationship between fuel blend and gasoline combustion products.  相似文献   

7.
Abstract

Consumer products can emit significant quantities of terpenes, which can react with ozone (O3). Resulting byproducts include compounds with low vapor pressures that contribute to the growth of secondary organic aerosols (SOAs). The focus of this study was to evaluate the potential for SOA growth, in the presence of O3, following the use of a lime-scented liquid air freshener, a pine-scented solid air freshener, a lemon-scented general-purpose cleaner, a wood floor cleaner, and a perfume. Two chamber experiments were performed for each of these five terpene-containing agents, one at an elevated O3 concentration and the other at a lower O3 concentration. Particle number and mass concentrations increased and O3 concentrations decreased during each experiment. Experiments with terpene-based air fresheners produced the highest increases in particle number and mass concentrations. The results of this study clearly demonstrate that homogeneous reactions between O3 and terpenes from various consumer products can lead to increases in fine particle mass concentrations when these products are used indoors. Particle increases can occur during periods of elevated outdoor O3 concentrations or indoor O3 generation, coupled with elevated terpene releases. Human exposure to fine particles can be reduced by minimizing indoor terpene concentrations or O3 concentrations.  相似文献   

8.
Abstract

A photochemical smog model system, the Variable-Grid Urban Airshed Model/Systems Applications International Mesoscale Model (UAM-V/SAIMM), was used to investigate photochemical pollution in the Bangkok Metropolitan Region (BMR). The model system was first applied to simulate a historical photochemical smog episode of two days (January 13-14, 1997) using the 1997 anthropogenic emission database available at the Pollution Control Department and an estimated biogenic emission. The output 1-hr ozone (O3) for BMR, however, did not meet the U.S. Environmental Protection Agency suggested performance criteria. The simulated minimum and maximum O3 values in the domain were much higher than the observations. Multiple model runs with different precursor emission reduction scenarios showed that the best model performance with the simulated 1-hr O3 meeting all the criteria was obtained when the volatile organic compound (VOC) and oxides of nitrogen (NOx) emission from mobile source reduced by 50% and carbon monoxide by 20% from the original database. Various combinations of anthropogenic and biogenic emissions in Bangkok and surrounding provinces were simulated to assess the contribution of different sources to O3 pollution in the city. O3 formation in Bangkok was found to be more VOC-sensitive than NOx-sensitive. To attain the Thailand ambient air quality standard for 1-hr O3 of 100 ppb, VOC emission in BMR should be reduced by 50-60%. Management strategies considered in the scenario study consist of Stage I, Stage II vapor control, replacement of two-stroke by four-stroke motorcycles, 100% compressed natural gas bus, 100% natural gas-fired power plants, and replacement of methyltertiarybutylether by ethanol as an additive for gasoline.  相似文献   

9.
ABSTRACT

Nonthermal plasma chemical decomposition of bromomethane (CH3Br) was investigated with a coaxial type packed-bed plasma reactor. It has been demonstrated that plasma chemical processing is an effective approach to decompose CH3Br in a wide concentration range. It has been shown that CH3Br decomposition reactivity depends on reactor operating factors such as background gas, O2 concentration, and humidification. Higher decomposition efficiencies can be obtained in dry N2. However, organic byproducts such as BrCN are concurrently produced under deaerated conditions. Water suppresses CH3Br decomposition and also affects the yields of COx (CO and CO2) and organic byproducts due to the involvement of some active species generated from water. The presence of O2 retards CH3Br decomposition by quenching high-energy electrons, while it suppresses organic byproducts and improves COx yield. The reacted carbons in CH3Br are recovered as COx almost quantitatively in air. Higher CO2 selectivities cannot be achieved by increasing O2 concentration. NOx formation, which is accompanied by CH3Br decomposition, can be effectively suppressed by decreasing O2 concentration down to 2%. Furthermore, reaction mechanisms are discussed by comparing the reactivities of CH3Br and its congeners.  相似文献   

10.
Abstract

An analysis of ozone (O3) concentrations and several other air quality-related variables was performed to elucidate their relationship with visibility at five urban and semi-urban locations in the southeast United States during the summer seasons of 1980-1996. The role and impact of O3 on aerosols was investigated to ascertain a relationship with visibility. Regional trend analysis over the 1980s reveals an increase in maximum O3 concentration coupled with a decrease in visibility. However, a similar analysis for the 1990s shows a leveling-off of both O3 and visibility; in both cases, the results were not statistically significant at the 5% level. A case study of site-specific trends at Nashville, TN, followed similar trends. To better understand the relationships between O3 concentration and visibility, the analysis was varied from yearly through daily to hourly averaged values. This increased temporal resolution showed a statistically significant inverse relationship between visibility and O3. Site-specific hourly r2 values ranged from 0.02 to 0.43. Additionally, by performing back-trajectory analysis, it was found that the visibility degraded by air mass migration over polluted areas.  相似文献   

11.
Abstract

A microwave-induced, steam/Ar/O2 , plasma “torch” was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N2 can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NOx ) is avoided in the plasma.

The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O2 and steam.The O2 was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500–600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O2 was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.  相似文献   

12.
Abstract

The U.S. Environmental Protection Agency has established a federal reference method (FRM) for ozone (O3) and allowed for designation of federal equivalent methods (FEMs). However, the ethylene‐chemiluminescence FRM for O3 has been replaced by the UV photometric FEM by most state and local monitoring agencies because of its relative ease of operation. Accumulating evidence indicates that the FEM is prone to bias under the hot, humid, and stagnant conditions conducive to high O3 formation. This bias may lead to overreporting hourly O3 concentrations by as much as 20–40 ppb. Measurement bias is caused by contamination of the O3 scrubber, a problem that is not detected by dry air calibration. An adequate wet test has not been codified, although a procedure has been proposed for agency consideration. This paper includes documentation of laboratory tests quantifying specific interferant responses, collocated ambient FRM/FEM monitoring results, and smog chamber comparisons of the FRM and FEMs with alternative scrubber designs. As the numbers of reports on monitor interferences have grown, interested parties have called for agency recognition and correction of these biases.  相似文献   

13.
Air sparging and soil vapor extraction (AS/SVE) are innovative remediation techniques that utilize volatilization and microbial degradation to remediate petroleum spills from soils and groundwater. This in situ study investigated the use of AS/SVE to remediate a gasoline spill from a leaking underground storage tank (UST) in the low permeability, clayey soil of the Appalachian Piedmont. The objectives of this study were to evaluate AS/SVE in low permeability soils by quantifying petroleum mass removal rates, monitoring vadose zone contaminant levels, and comparing the mass extraction rates of continuous AS/SVE to 8 and 24 h pulsed operation. The objectives were met by collecting AS/SVE exhaust gas samples and vadose zone air from multi-depth soil vapor probes. Samples were analyzed for O2, CO2, BTEX (benzene, toluene, ethylbenzene, xylene), and total combustible hydrocarbon (TCH) concentrations using portable hand meters and gas chromatography. Continuous AS/SVE was effective in removing 608 kg of petroleum hydrocarbons from low permeability soil in 44 days (14.3 kg day−1). Mass removal rates ranged from 2.6 times higher to 5.1 times lower than other AS/SVE studies performed in sandy sediments. BTEX levels in the vadose zone were reduced from about 5 ppm to 1 ppm. Ten pulsed AS/SVE tests removed 78 kg in 23 days and the mean mass removal rate (17.6 kg day−1) was significantly higher than the last 15 days of continuous extraction. Pulsed operation may be preferable to continuous operation because of increased mass removal and decreased energy consumption.  相似文献   

14.
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 NOx, 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.  相似文献   

15.
Abstract

Environmental agencies are currently in the process of implementing a new air management program, which includes the improvement of fuel quality. In this work, exhaust emissions data and estimated relative risk for various fuels testing in-use vehicles, equipped with three different exhaust emission control technologies, are presented. Aromatics, sulfur, and olefins contents; type of oxygenated compound; and Reid vapor pressure were varied. The aim also includes calculating the ozone (O3)of forming potential and a relative cancer risk of emissions from current and formulated gasoline blends in Mexico. The proposed gasoline decreases carbon monoxide, total hydrocarbons (THC), and nitrogen oxides emissions by 18 and 14%, respectively, when compared with gasoline sold in the rest of the country and within ozone nonattainment metropolitan areas in Mexico, respectively.  相似文献   

16.
Abstract

In the In-Duct Injection Process, a lime slurry is sprayed into the flue gas between the air preheater and solids collection equipment, and about 30-60 percent removal of SO2 is achieved. A simple model of this process has been developed based on heat and mass transfer theories, and this model was fitted to the data obtained at proof-of-concept test units. Data taken with separate injection of dry lime and water were also modeled, but the SO2 removal was less than for slurry injection, probably because of incomplete capture of lime particles by the water droplets.  相似文献   

17.
A study of the effect of water vapor on the photochemical system NO2 + alphapinene + hv was conducted. A Hotpack Environmental Room was used as a constant temperature chamber, a bank of ultraviolet and fluorescent lamps as a source of simulated solar radiation, and a 150-liter FEP Teflon bag as a reaction vessel. Representative concentrations of 10 pphm NO2 and 50 pphm alphapinene were used in a 3 × 2 × 2 factorial design where absolute humidities of 0.0000, 0.0090, 0.01 80 g H2O/g dry air were varied.

Matheson zero air was passed through a clean air train and used as the diluent. Nitrogen dioxide was added to the reaction mixture by a permeation tube, and water and alpha-pinene by evaporation techniques.

Variables measured as a function of time over a 2-hour irradiation period were total oxidants (Mast Ozone Meter), condensation nuclei (General Electric Small Particle Detector), ozone (Regener Chemiluminescent Ozone Meter), nitrogen dioxide and nitric oxide (Technicon Autoanalyzer), and alpha-pinene (Perkin- Elmer Model 800 gas chromatograph).

Upon irradiation, systems containing nitrogen dioxide and alpha-pinene formed oxidants, ozone, condensation nuclei, and nitric oxide. Based on the differences between simultaneous oxidant and ozone measurements, the formation of peroxide- like compounds may be inferred. During the course of the irradiation, nitrogen dioxide and alpha-pinene were consumed. The concentration-time profiles of all variables were characteristic of those exhibited by typical photochemical smog systems.

An effect of water vapor on the systems studied was demonstrated. Increasing humidity decreased net mean/time oxidant and ozone production and net maximum condensation nuclei production. These effects were significant at a 0.05 confidence level. Effects of water on average mean/time NO2, NO, and alphapinene concentrations were insignificant at this level. The oxidant to ozone ratio was found to decrease with increasing humidity.

The significant decreases in net oxidant and ozone production and NO2 consumption with increasing water vapor concentration in systems of nitrogen dioxide alone, suggests that water manifests an effect on pertinent inorganic reactions, and the data also suggest additional water participation in the organic reactions.  相似文献   

18.
ABSTRACT

In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H2O2 with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H2O2 into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H2O2 within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H2O2. The decomposition rates of H2O2 were determined using both equilibrated water samples and soil slurries. Results showed H2O2 decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.  相似文献   

19.
Abstract

The removal system for the absorption of CO2 with amines and NH3 is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO2 by amines and NH3 solutions was performed in this study to derive the reaction kinetics. The absorption of CO2 as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH3 was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O2 concentration and pH value. The absorption efficiency of MEA is better than that of NH3 and DEA, but the absorption capacity of NH3 is the best. The active energies of the MEA and NH3 with CO2 are 33.19 and 40.09 kJ/mol, respectively.  相似文献   

20.
ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF6) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H2SO4. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF6 dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF6 concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF6 dissociation, mainly H2SO4, SO2, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF6, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF6 concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF6 concentration is kept at a low ppb level.  相似文献   

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