Kinetics of catalytic oxidation of benzene, n-hexane, and emission gas from a refinery oil/water separator over a chromium oxide catalyst

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 degrees 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.     

Decomposition of volatile organic compounds using gliding arc discharge plasma

ABSTRACT

This work provides a systematic review on the decomposition of volatile organic pollutants in flue gas through the gliding arc (GA) plasma technology. To begin with, the basic mechanisms of GA plasma generation are summarized and three characteristic stages existed during the GA plasma generation process are revealed: gas breakdown stage, equilibrium stage, and non-equilibrium stage. Then, the types of GA reactors are comparatively illustrated. Possible destruction mechanisms of volatile organic compounds (VOCs) by GA plasma are discussed by taking chloroform, benzene, and methanol as examples. Furthermore, the effects of many operating parameters on the VOCs destruction efficiency are comprehensively analyzed. Simultaneously, the product distribution, energy cost, technical and economic during the whole decomposition process are considered. Finally, the advantages and disadvantages of GA plasma and its further development trend are concluded from the academic and industrial application of GA plasma in VOCs decomposition.

Implications: This paper comprehensively describes the principle, characteristics, research progress and engineering application examples of the degradation of volatile organics by gliding arc discharge plasma, so that readers can fully understand the degradation of volatile organics by gliding arc discharge plasma and provide theoretical basis for the industrial application of the degradation of volatile organics by gliding arc discharge plasma.     

Performance Characteristics of a Regenerative Catalytic Oxidizer for Treating VOC-Contaminated Airstreams

ABSTRACT

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. × 200-cm height regenerative beds was used to treat methyl ethyl ketone (MEK) and toluene, respectively, in an airstream. The regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m²/m³, and specific heat capacity 840 J/kg °C) as a solid regenerative material and K-type thermal couples for measuring solid and gas temperatures, respectively. The catalyst bed temperature was kept around 400 °C and the gas superficial velocity was operated at 0.234 m/sec. This investigation measured and analyzed distributions of solid and gas temperatures with operating time and variations of volatile organic compound (VOC) concentrations in the regenerative beds. The overall VOC removal efficiency exceeded 98% for MEK and 95% for toluene. Degradation of VOCs will exist for MEK on the surface of solid material (gravel) in the temperature range of 330-400 °C, but toluene does not exhibit this phenomenon.     

Catalytic oxidation for air pollution control

Bench-scale experiments have been conducted to evaluate a series of titania-supported Pt-Pd (as oxides) catalysts in the presence and absence of MoO₃ and Fe₂O₃ additives for their effectiveness in the complete catalytic oxidation of volatile organic compounds (VOCs) in air likely to be found in waste gases. Under oxidizing conditions, all of the catalysts promoted the complete oxidation of VOCs to CO₂ and H₂O. 99 % Conversion was achieved with a C₂H₄-C₂H₆ gas mixture in air at temperatures between about 160–450 °C and at a space velocity of 20,000 h^?1. Oxidation activity for the titania supported catalysts were found to decrease in the order Pt-Pd-Mo-Fe > Pt-Pd-Mo > Pt-Pd-Fe > Pt-Pd. However, the addition of MoO₃ and Fe₂O₃ increase the catalyst activity and reduce the reaction temperature for the complete destruction. Ageing was also performed in order to study the stability of the most active catalyst. Pt-Pd-Mo-Fe (as oxides) on titania catalyst is effective in oxidizing a wide range of volatile organic compounds at relatively low temperatures (220–405 °C) and and at a space velocity of 40,000 h^?1 and is resistant to poisoning by halogenated and amine volatile organic compounds.     

Thermal and Catalytic Incinerators for the Control of VOCs

Abstract

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

Multiple comparisons of organic,microbial, and fine particulate pollutants in typical indoor environments: Diurnal and seasonal variations

This study was performed to investigate the possible sources as well as seasonal and diurnal variations of indoor air pollutants in widely used four different environments (house, office, kindergarten, and primary school) in which people spend most of their time. Bioaerosol levels and species, volatile organic compound (VOC) levels, and PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) levels were determined in different parts of these environments in parallel with outdoor sampling. Air pollution samplings were carried out in each microenvironment during five subsequent days in both winter and summer in Ankara, Turkey. The results indicated that bioaerosol, VOC, and PM_2.5 levels were higher in the winter than in the summer. Moreover, PM_2.5 and bioaerosol levels showed remarkable daily and diurnal variations, whereas a good correlation was found between the VOC levels measured in the morning and in the afternoon. Bacteria levels were, in general, higher than fungi levels. Among the VOCs, toluene was the most predominant, whereas elevated n-hexane levels were also observed in the kindergarten and the primary school, probably due to the frequent wet cleaning during school days. According to factor analysis, several factors were found to be significantly influencing the indoor air quality (IAQ), and amongst them, VOC-based products used indoors ranked first. The overall results indicate that grab sampling in naturally ventilated places may overestimate or underestimate the IAQ due to the inhomogeneous composition of indoor air caused by irregular exchanges with the outdoor air according to the season and/or occupants' habits.

Implications Seasonal and diurnal variations of VOCs, PM_2.5, bioaerosols in house, office, and schools were observed, in which PM_2.5 and bioaeorosols showed marked both intra- and interday variability, but VOCs did not. VOC-containing products were the most common source of air pollutants affecting the indoor air quality. External factors affecting the indoor air quality were season and indirectly ventilation. A grab sample cannot be representative in evaluating the air quality of a naturally ventilated environment precisely.     

Formaldehyde Concentrations Inside Private Residences: A Mail-Out Approach to Indoor Air Monitoring

Abstract

The main objective of this study was to monitor the volatile organic compounds (VOCs) in the stack gas released from organic chemical industrial plants to determine emission factors. Samples from 52 stacks, with or without air pollution control devices (APCDs), from seven industrial processes were taken and VOCs measured using U.S. Environmental Protection Agency (EPA) Method 18. These 7 processes, including 26 plants, were the manufacturers of acrylonitrile–butadiene–styrene (ABS), polyvinyl chloride (PVC), polystyrene (PS), acrylic resin (ACR), vinyl chloride (VC), para–terephthalic acid (PTA), and synthetic fiber (SYF). The results clearly indicate significant variations of emission factors among the various industrial processes, particularly emission factors for those without APCDs. As expected, those with APCDs yield much less emission factors. Regardless of those with or without APCDs, the order of manufacturing processes with regard to VOC emission factors is SYF > ABS > PS > ACR > PTA > PVC > VC. The emission factors for some processes also differ from those in EPA–42 data file. The VOC profiles further indicate that some VOCs are not listed in the U.S. VOC/Particulate Matter Speciation Data System (SPECIATE). The potential O₃ formation is determined from the total amount of VOC emitted for each of seven processes. The resultant O₃ yield varied from 0.22 (ACR) to 2.33 g O₃ g^–1 VOC (PTA). The significance of this O₃ yield is discussed.     

Incinerating Volatile Organic Compounds with Ferrospinel Catalyst MnFe2O4: An Example with Isopropyl Alcohol

Abstract

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe₂O₄. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe₃O₄]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr^?1, an oxygen (O₂) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 °C.     

Four Common Diagnostic Problems that Inhibit Radon Mitigation

Abstract

An activated sludge aeration tank (40 × 40 × 300 cm, width × length × height) with a set of 2-mm orifice air spargers was used to treat gas-borne volatile organic compounds (VOCs; toluene, p-xylene, and dichloromethane) in air streams. The effects of liquid depth (Z), aeration intensity (G/A), the overall mass-transfer rate of oxygen in clean water (K _L a _O2 ), the Henry’s law constant of the tested VOC (H), and the influent gaseous VOC concentration (C ₀) on the efficiency of removal of VOCs were examined and compared with a literature-cited model. Results show that the measured VOC removal efficiencies and those predicted by the model were comparable at a G/A of 3.75–11.25 m³/m²·hr and C ₀ of ～1000–6000 mg/m³. Experimental data also indicated that the designed gas treatment reactor with K _L a _O2 = 5–15 hr^?1 could achieve >85% removal of VOCs with H = 0.24–0.25 at an aerated liquid depth of 1 m and >95% removal of dichloromethane with H = 0.13 at a 1-m liquid depth.     

Weekday/Weekend Differences in OH Reactivity with VOCs and CO in Baltimore,Maryland

ABSTRACT

This study compared the first-order frequencies for OH associated with volatile organic compounds (VOCs) and CO (hereafter called OH reactivity with VOCs or CO), the product of the VOC or CO concentration, and their respective k_OH value, on an average weekday with that on an average weekend day at a core urban site in Baltimore, MD. The average daytime concentrations were calculated for each of the 55 available Photochemical Assessment Monitoring Station (PAMS) VOCs using data from the Baltimore site. The data were sorted in descending order to highlight the important species based on concentration. The OH reactivity with VOCs was sorted in descending order to identify the important species based on the magnitude of the OH reactivity. A similar process was followed for the OH reactivity with CO. The contribution of the significant species to the weekday/weekend difference in OH reactivity was examined.

The OH reactivity with C₅H₈ was the largest among the OH reactivity with the PAMS' VOCs and was the same on the weekday and weekend. The weekday/weekend difference in OH reactivity with VOCs was entirely due to differences in concentrations of the anthropogenic VOCs. The OH reactivity with VOCs was 11% larger on the weekday. When OH reactivity with CO was included, the OH reactivity was 13% larger on the weekday.     

Interlaboratory Study of a Test Method Measuring Total Volatile Organic Compound Content of Consumer Products

Abstract

Consumer products are potentially significant sources of volatile organic compounds (VOCs), which are precursors to the formation of ozone in photochemical smog. To address the problem of ozone formation in ambient air, the U.S. Environmental Protection Agency (EPA) has been involved in the development of test methods for measuring the VOC content of consumer products. This paper describes results of an interlaboratory study to estimate the repeatability (precision of analyses performed by a single laboratory) and reproducibility (precision of analyses performed by different laboratories) of the consumer products’ VOC measurement method based on EPA Method 24 (for VOCs in surface coatings).

The mean method repeatability was 2.7 wt % VOC, and the mean method reproducibility was 4.8 wt % VOC. Method repeatability ranged from 0.2 to 4.4 wt % VOC, and reproducibility ranged from 0.6 to 11.9 weight percent VOC. The precision of the VOC method for consumer

products is similar to the precision of EPA Method 24 for surface coatings.     

Source Location and Characterization of Volatile Organic Compound Emissions at a Petrochemical Plant in Kaohsiung,Taiwan

Abstract

This paper elucidated a novel approach to locating volatile organic compound (VOC) emission sources and characterizing their VOCs by database and contour plotting. The target of this survey was a petrochemical plant in Linyan, Kaohsiung County, Taiwan. Samples were taken with canisters from 25 sites inside this plant, twice per season, and analyzed by gas chromatography–mass spectrometry. The survey covered 1 whole year. By consolidated into a database, the data could be readily retrieved, statistically analyzed, and clearly presented in both table and graph forms. It followed from the cross‐analysis of the database that the abundant types of VOCs were alkanes, alkenes/dienes, and aromatics, all of which accounted for 99% of total VOCs. By contour plotting, the emission sources for alkanes, aromatics, and alkenes/dienes were successfully located. Through statistical analysis, the database could provide the range and 90% confidence interval of each species from each emission source. Both alkanes and alkene/dienes came from tank farm and naphtha cracking units and were mainly composed of C₃–C₅ members. Regarding aromatics, benzene, toluene, and xylenes were the primary species; they were emitted from tank farm, aromatic units, and xylene units.     

Volatile organic compound emissions from municipal solid waste disposal sites: A case study of Mumbai,India

Improper solid waste management leads to aesthetic and environmental problems. Emission of volatile organic compounds (VOCs) is one of the problems from uncontrolled dumpsite. VOCs are well known to be hazardous to human health and many of them are known or potential carcinogens. They also contribute to ozone formation at ground level and climate change as well. The qualitative and quantitative analysis of VOCs emitting from two municipal waste (MSW) disposal sites in Mumbai, India, namely Deonar and Malad, are presented in this paper. Air at dumpsites was sampled and analyzed on gas chromatography–mass spectrometry (GC-MS) in accordance with U.S. Environmental Protection Agency (EPA) TO-17 compendium method for analysis of toxic compounds. As many as 64 VOCs were qualitatively identified, among which 13 are listed under Hazardous Air Pollutants (HAPs). Study of environmental distribution of a few major VOCs indicates that although air is the principal compartment of residence, they also get considerably partitioned in soil and vegetation. The CO₂ equivalent of target VOCs from the landfills in Malad and Deonar shows that the total yearly emissions are 7.89E+03 and 8.08E+02 kg, respectively. The total per hour ozone production from major VOCs was found to be 5.34E-01 ppb in Deonar and 9.55E-02 ppb in Malad. The total carcinogenic risk for the workers in the dumpsite considering all target HAPs are calculated to be 275 persons in 1 million in Deonar and 139 persons in 1 million in Malad.

Implications: This paper describes the hazards of VOC emission from open dumpsites, a common practice, in an Indian metro city. The subsequent partitioning of the emitted VOCs in other environmental compartment from air is presented. The global warming potential and the health hazards to the dumpsite workers from the emitted VOCs have also been estimated.     

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.     

Performance characteristics of a regenerative catalytic oxidizer for treating VOC-contaminated airstreams

A pilot apparatus of a regenerative catalytic oxidizer (RCO) equipped with two electrical heaters and two 20-cm i.d. x 200-cm height regenerative beds was used to treat methyl ethyl ketone (MEK) and toluene, respectively, in an airstream. The regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m2/m3, and specific heat capacity 840 J/kg degree C) as a solid regenerative material and K-type thermal couples for measuring solid and gas temperatures, respectively. The catalyst bed temperature was kept around 400 degrees C and the gas superficial velocity was operated at 0.234 m/sec. This investigation measured and analyzed distributions of solid and gas temperatures with operating time and variations of volatile organic compound (VOC) concentrations in the regenerative beds. The overall VOC removal efficiency exceeded 98% for MEK and 95% for toluene. Degradation of VOCs will exist for MEK on the surface of solid material (gravel) in the temperature range of 330-400 degrees C, but toluene does not exhibit this phenomenon.     

Measurements show that marginal wells are a disproportionate source of methane relative to production

ABSTRACT

Oil and natural gas wells are a prominent source of the greenhouse gas methane (CH₄), but most measurements are from newer, high producing wells. There are nearly 700,000 marginal “stripper” wells in the US, which produce less than 15 barrels of oil equivalent (BOE) d^?1. We made direct measurements of CH₄ and volatile organic carbon (VOC) emissions from marginal oil and gas wells in the Appalachian Basin of southeastern Ohio, all producing < 1 BOE d^?1. Methane and VOC emissions followed a skewed distribution, with many wells having zero or low emissions and a few wells responsible for the majority of emissions. The average CH₄ emission rate from marginal wells was 128 g h^?1 (median: 18 g h^?1; range: 0– 907 g h^?1). Follow-up measurements at five wells indicated high emissions were not episodic. Some wells were emitting all or more of the reported gas produced at each well, or venting gas from wells with no reported gas production. Measurements were made from wellheads only, not tanks, so our estimates may be conservative. Stochastic processes such as maintenance may be the main driver of emissions. Marginal wells are a disproportionate source of CH₄ and VOCs relative to oil and gas production. We estimate that oil and gas wells in this lowest production category emit approximately 11% of total annual CH₄ from oil and gas production in the EPA greenhouse gas inventory, although they produce about 0.2% of oil and 0.4% of gas in the US per year.

Implications: Low producing marginal wells are the most abundant type of oil and gas well in the United States, and a surprising number of them are venting all or more of their reported produced gas to the atmosphere. This makes marginal wells a disproportionate greenhouse gas emissions source compared to their energy return, and a good target for environmental mitigation.     

The Role of Viscosity in Fabric Filtration

Abstract

An approach for measuring point-source emissions of volatile organic compounds (VOCs), acidic vapors, and other species is presented. The amount emitted is determined by directly measuring the actual weight gain of an adsorbent bed over a period of time, which is a cumulative rather than a grabbed sample. As a result, wide fluctuations of concentration and erratic flow behavior during sampling are accommodated with no apparent effect on the accuracy of the measured emission rate. The emission rate is determined by a mass balance including the mass change of the sorbent, as well as the influent and effluent humidities.

Validation tests used a known mass flow rate of vapor in a carrier gas, which was compared with the amount measured. The vapor was a single VOC, a mixture of VOCs, or a mixture of a VOC with water. Conditions studied were the compound or mixture of compounds, concentration, carrier gas, flow rate, and adsorbent. In some tests the VOC was admitted intermittently. The VOCs included n-hexane, acetone, toluene, vinyl acetate, and 1,1,1 trichloroethane. For 105 tests, the average absolute discrepancy of the delivered and measured emission rates was 6.8% and the standard deviation was 3.4%.     

A New Method for the Rapid Determination of Volatile Organic Compound Breakthrough Times for a Sorbent at Concentrations Relevant to Indoor Air Quality

Abstract

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25% relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Investigation of partitioning mechanism for volatile organic compounds in a multiphase system

Laboratory experiments were performed to investigate the partitioning behavior of a set of diverse volatile organic compounds (VOCs). After equilibration at a temperature of 25 °C, the VOC concentrations were measured by headspace method in combination with gas chromatography/mass spectrometry (GC/MS). The obtained data were used to determine the partition coefficients (K_P) of VOCs in a gas-liguid-solid system. The results have shown that the presence and nature of solid materials in the working solution control the air-water partitioning of dissolved VOCs. The air/solution partitioning of BTEX and C₉-C₁₀ aldehydes was most affected in the presence of diesel soot. K_P values decreased by a factor ranging from 1.5 for toluene to 3.0 for ethylbenzene. The addition of mineral dust in the working solution exhibited greater influence on the partitioning of short aldehydes. K_P values decreased by a factor of 1.8. The experimental partition coefficients were used to develop a predictive model for partitioning of BTEX and n-aldehydes between air, water and solid phases.     

An Evaluation of Emissions and Control Technologies for the Metal Decorating Process

A simple but effective sampling and analytical procedure is described for determining total organics, carbon dioxide, carbon monoxide, and methane emitted from web offset printing presses. Data are reported on a number of controlled and uncontrolled sources and emission levels are related to process variables such as press speed, ink coverage and dryer type. For controlled sources employing either catalytic or thermal incineration units, conversion efficiencies are reported as a function of temperature. Operational curves are presented for each control system studied indicating the dependency of carbon dioxide, NO_xt and organic output to incineration temperatures.