Microwave Plasma Conversion of Volatile Organic Compounds

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 (NO_x ) 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.     

Adsorption and Desorption Characteristics of Semiconductor Volatile Organic Compounds on the Thermal Swing Honeycomb Zeolite Concentrator

Abstract

The use of a honeycomb zeolite concentrator and an oxidation process is one of the most popular methods demonstrated to control volatile organic compound (VOCs) emissions from waste gases in semiconductor manufacturing plants. This study attempts to characterize the performance of a concentrator in terms of the removal efficiencies of semiconductor VOCs (isopropyl alcohol [IPA], acetone, propylene glycol methyl ether [PGME], and propylene glycol monomethyl ether acetate [PGMEA]) under several parameters that govern the actual operations. Experimental results indicated that at inlet temperatures of under 40 °C and a relative humidity of under 80%, the removal efficiency of a zeolite concentrator can be maintained well over 90%. The optimal rotation speed of the concentrator is between 3 and 4.5 rph in this study. The optimal rotation speed increases with the VOCs inlet concentration. Furthermore, reducing the concentration ratio helps to increase the removal efficiency, but it also increases the incineration cost. With reference to competitive adsorption, PGMEA and PGME are more easily adsorbed on a zeolite concentrator than are IPA and acetone because of their high boiling points and molecular weights.     

Destruction of Volatile Organic Compounds Using Catalytic Oxidation

Catalytic oxidation is an air pollution control technique in which volatile organic compounds (VOCs) and vapor-phase air toxics in an air emission stream are oxidized with the help of a catalyst Design of catalytic systems for control of point source emissions is based on stream-specific characteristics and desired control efficiency. This paper discusses the key emission stream characteristics and VOC characteristics that affect the applicability of catalytic oxidation. The application of catalytic oxidation technology to four types of air emission sources is discussed: (1) groundwater stripping operations; (2) graphic arts facilities; (3) flexographic printing plants; and (4) latex monomer production. The characteristics of each of these emissions are discussed along with the catalytic technology used to control these emissions.     

Partition of Volatile Organic Compounds in Activated Sludge and Wastewater

Abstract

The Henry’s law constant is important in the gas-liquid mass transfer process. Apparent dimensionless Henry’s law constant, or the gas-liquid partition coefficient (K’ _H), for both hydrophilic (methanol, isopropyl alcohol, and acetone) and hydrophobic (toluene and p-xylene) organic compounds in deionized (DI) water, a wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L were measured using the single equilibrium technique at 293 K.

Experimental results demonstrate that the K’ _H of any of the test volatile organic compounds varied among three situations. First, the K’_H of the hydrophilic compounds in mixed liquor with the maximum SS concentration was 9–21% higher than those in DI water. Second, those for toluene and p-xylene were 77% and 93% lower, respectively, in the mixed liquor with the maximum SS concentration. Third, the K’_H values of all of the test compounds in the wastewater were only 10% lower than those in DI water.

A model was developed to relate K’ _H with wastewater DOC and the SS concentration in the activated sludge using an organic carbon-water partition coefficient and activated sludge-water partition coefficient as model parameters. The model was verified and model parameters for test compounds estimated.     

Measuring Concentrations of Volatile Organic Compounds in Vinyl Flooring

ABSTRACT

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics.

To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m² section of new VF was punched randomly to produce ~200 0.78-cm² disks. The disks were milled to a powder at -140 °C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatog-raphy/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 |ig/g VF for n-hexadecane to 130 |Jg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

Emission Characteristics of Volatile Organic Compounds from Semiconductor Manufacturing

Abstract

A huge amount of volatile organic compounds (VOCs) is produced and emitted with waste gases from semiconductor manufacturing processes, such as cleaning, etching, and developing. VOC emissions from semiconductor factories located at Science-Based Industrial Park, Hsin-chu, Taiwan, were measured and characterized in this study. A total of nine typical semiconductor fabricators (fabs) were monitored over a 12-month period (October 2000-September 2001). A flame ionization analyzer was employed to measure the VOC emission rate continuously in a real-time fashion. The amount of chemical use was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County as per the regulation of the Taiwan Environmental Protection Administration. The VOC emission factor, defined as the emission rate (kg/month) divided by the amount of chemical use (L/month), was determined to be 0.038 ± 0.016 kg/L. A linear regression equation is proposed to fit the data with the correlation coefficient (R²) = 0.863. The emission profiles of VOCs, which were drawn using the gas chromatograph/mass spectrometer analysis method, show that isopropyl alcohol is the dominant compound in most of the fabs.     

Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Sources of Volatile Organic Compounds in a University Building

A total of 34 volatile organic compounds (VOCs) were measured in the indoor of laboratories, offices and classrooms of the Chemical Engineering Department of Hacettepe University in Ankara in 2 week-day passive sampling campaigns. The average concentrations ranged from 0.77 to 265 μg m^?3 at the different indoor sites, with the most abundant VOC found to be toluene (119.6 μg m^?3), followed by styrene (21.24 μg m^?3), 2-ethyltoluene (17.11 μg m^?3), n-hexane (10.21 μg m^?3) and benzene (9.42 μg m^?3). According to the factor analysis, the evaporation of solvents used in the laboratories was found to be the dominant source.     

Thermal Oxidation Kinetics of Selected Organic Compounds

A thermal oxidizer destroys organic pollutants by oxidation to CO₂ and water. Time, temperature, and turbulence, govern the performance of a thermal oxidizer just as they do all other combustion devices. To achieve a desired degree of destruction, a higher temperature allows the use of a shorter residence time and vice versa. For most organics, a thermal oxidizer designed at 1400°-1500°F with 0.1 to 0.3 seconds residence time is normally enough to obtain nearly complete destruction.¹ However, some chemicals require more extreme conditions. These time-temperature requirements can be determined from kinetic rate studies.     

An Investigation of Odors and Volatile Organic Compounds Released during Composting

ABSTRACT

The emissions of odors and volatile organic compounds produced from a commercial composting operation have been studied using a laboratory-scale composting system. The composting activity of a typical commercial compost feed was followed by monitoring the composting temperature, as well as the respiratory rate. Using a controlled aeration system, the gaseous volatiles produced were tested for odors using the "dilution-to-threshold" method, as well as gas composition, as determined by gas chromatography-mass spectrometry.

The results indicated that while there may be a reasonable correlation between the release of volatile organic compounds (VOCs) and odors, care has to be taken when trying to identify offensive odors with specific chemical species. However, the data obtained suggests that offensive odors formed during commercial composting may be due to sulfurous and nitrogenous compounds, although their concentrations in the compost gases may not be very high.

The major release of VOCs occurred during the first two weeks of composting, after which the gaseous releases fell dramatically as the composting process proceeded and temperatures started to fall.     

机动车尾气VOCs排放特征及减排措施研究

分析了机动车尾气挥发性有机物(VOCs)的排放特征,发现尾气VOCs排放具有明显的日变化和季节变化特征。不同区域不同车型机动车尾气VOCs成分谱略有差异,轻型汽油车尾气VOCs中芳香烃和烷烃含量较高,柴油车烷烃含量较高。尾气排放受机动车保有量、行驶里程、维护保养水平、行驶速度和燃油标准、排放标准等因素影响。从优先控制汽油车、加快机动车更新、采取本地化减排措施、加强多元管理措施、提高科研水平等方面提出了针对性的减排措施。     

Total Volatile Organic Compounds in the Urban Environment of Delhi

ABSTRACT

Total volatile organic compounds (TVOCs) in the urban ambient environment of Delhi were monitored from November 1994 to June 1995 at 13 sites using an inexpensive and a manual-labor-intensive sample collection procedure in want of sophisticated equipment. The results of the study show appreciable levels of TVOCs in the ambient environment of Delhi. The amount of TVOCs in the ambient environment was found to vary between 3 and 42 ppmv and exhibited wide temporal and seasonal variations. On a diurnal cycle, TVOC levels mostly peaked at 9:00 a.m., which coincided with the peak traffic hour. TVOC buildup in the urban atmosphere has serious implications for air quality through the formation of highly toxic oxidants. The results of this preliminary study make out a strong case for a regular monitoring of TVOCs in the urban environment of Delhi.     

Photocatalytic Oxidation of Volatile Organic Compounds Using Fluorescent Visible Light

Abstract

Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a highly attractive alternative technology for purification and deodorization of indoor air. The main objectives of this study were to demonstrate that a common fluorescent visible light (FVL) lamp can be used to effectively remove by PCO low concentrations of VOCs from slightly contaminated air and to provide some fundamental and technical details on the process. The target VOC was n-butanol, which is a standard reference odorant. Its PCO was studied under a long residence time in a 3.7-L cylindrical reactor with commercial titanium dioxide (TiO₂) as the reference photocatalyst and using mostly FVL for illumination. For comparison only, a UV (black) light lamp was used. The gas-phase products were detected and quantified online by gas chromatography (GC). The effects of reactor residence time, of inlet concentration, and of the relative light intensity on the efficiency of the process were also evaluated. At a high n-butanol concentration (0.1 vol %), butanal and propanal were identified as the intermediate products of the process; ethanal appeared when the initial concentration was <850 ppm_v. This indicates that PCO leading to CO₂ and H₂O is relatively slow and proceeds in a stepwise manner. Although the efficiency of the process with an FVL lamp was significantly lower than when using a UV black light, complete PCO of low concentrations was achieved for 100 ppm_v. In a search for a material with photoactivation extended to higher wavelengths or increased photo-activity, several samples of transition metal- or silver ion-doped (2 atomic %) TiO₂ as well as SrTi_1xFe_xO₃ (x = 0.1 and 0.15) perovskites were included in the study. None of these materials was more active than pure TiO₂. The results of this study open new horizons in the area of indoor air quality (IAQ) control.     

Characterization of Emissions of Volatile Organic Compounds from Interior Alkyd Paint

ABSTRACT

Alkyd paint continues to be used indoors for application to wood trim, cabinet surfaces, and some kitchen and bathroom walls. Alkyd paint may represent a significant source of volatile organic compounds (VOCs) indoors because of the frequency of use and amount of surface painted. The U.S. Environmental Protection Agency (EPA) is conducting research to characterize VOC emissions from paint and to develop source emission models that can be used for exposure assessment and risk management. The technical approach for this research involves both analysis of the liquid paint to identify and quantify the VOC contents and dynamic small chamber emissions tests to characterize the VOC emissions after application. The predominant constituents of the primer and two alkyd paints selected for testing were straight-chain alkanes (C9–C12); C8–C9 aromatics were minor constituents. Branched chain alkanes were the predominant VOCs in a third paint. A series of tests were performed to evaluate factors that may affect emissions following application of the coatings. The type of substrate (glass, wallboard, or pine board) did not have a substantial impact on the emissions with respect to peak concentrations, the emissions profile, or the amount of VOC mass emitted from the paint. Peak concentrations of total volatile organic compounds (TVOCs) as high as 10,000 mg/m³ were measured during small chamber emissions tests at 0.5 air exchanges per hour (ACH). Over 90% of the VOCs were emitted from the primer and paints during the first 10 hr following application. Emissions were similar from paint applied to bare pine board, a primed board, or a board previously painted with the same paint. The impact of other variables, including film thickness, air velocity at the surface, and air-exchange rate (AER) were consistent with theoretical predictions for gas-phase, mass transfer-controlled emissions. In addition to the alkanes and aromatics, aldehydes were detected in the emissions during paint drying. Hexanal, the predominant aldehyde in the emissions, was not detected in the liquid paint and was apparently an oxidation product formed during drying. This paper summarizes the results of the product analyses and a series of small chamber emissions tests. It also describes the use of a mass balance approach to evaluate the impact of test variables and to assess the quality of the emissions data.     

Long-path FTIR Measurements of Volatile Organic Compounds in an Industrial Setting

A long-path Fourier transform spectrometer was used to make measurements of volatile organic compounds in an industrial complex in New Castle, Delaware as part of the Superfund Innovative Technology Evaluation (SITE) program. These data are compared to data taken with a whole-air canister technique. To provide an effective comparison the canisters were transported along the path for a 32-min period. For each FTIR spectrum, 256 interferograms were co-added over a 4-mln period. Eight individual spectra were then co-added to obtain the comparison data.     

Sources and Source Strengths of Volatile Organic Compounds in a New Office Building

This study was conducted at a newly constructed federal office building in Portland, Oregon. The primary objectives were to identify the major sources of volatile organic compounds (VOC) in the building and to measure both long-term (one year) and short-term (several day) variations in concentrations and source strengths. Samples for VOC were collected on four occasions over a period of 14 months starting with the first month of occupancy. During the final sampling period, samples were collected over four days (Friday - Monday). The samples were analyzed for individual compounds and for total VOC (TVOC). The results were expressed as specific source strengths, as well as concentrations, to facilitate comparisons of measurements made under different ventilation conditions.

The primary source of VOC in the building was identified as liquid-process photocopiers and plotters which emitted a characteristic mixture of C10-Cn isoparaffinic hydrocarbons. The specific source strength of TVOC, which was dominated by the emissions from these office machines, remained relatively constant over the course of the study. Motor vehicles in the below-ground parking garage were implicated as another major source of hydrocarbons in the building. Over the final four-day sampling period, the specific source strength of TVOC varied by about a factor of five, predominantly reflecting occupant use of office machines.     

Volatile Organic Compounds from Coal Tar and Soil Vapor Samples at MGP Sites

This study characterized organic compounds found in New York State manufactured gas plant (MGP) coal tar vapors using controlled laboratory experiments from four separate MGP sites. In addition, a limited number of deep (0.3–1.2 m above coal tar) and shallow (1.2–2.4 m above coal tar) soil vapor samples were collected above the in situ coal tar source at three of these sites. A total of 29 compounds were consistently detected in the laboratory-generated coal tar vapors at 50°C, whereas 24 compounds were detected at 10°C. The compounds detected in the field sample results were inconsistent with the compounds found in the laboratory-generated samples. Concentrations of compounds in the shallow soil vapor sample were either non-detectable or substantially lower than those found in deeper samples, suggesting attenuation in the vadose zone. Laboratory-generated data at 50°C compared the (% non-aromatic)/(% aromatic) ratio and indicated that this ratio may provide good discrimination between coal tar vapor and common petroleum distillates.     

吹脱-捕集气相色谱法测定底质中易挥发性有机物

研究并建立了利用吹脱－捕集气相色谱法测定底质中易挥发性有机物的分析方法。该方法对底质中２５种易挥发性有机物进行测定。方法回收率在９６％－１０５％,最低检出浓度在０．３－１４．５μｇ／ｋｇ,变异系数在２．７％－５．３％。