Decomposition of volatile organic compounds using corona discharge plasma technology

This paper explores the application of corona plasma technology as a tool in treatment of volatile organic compounds (VOCs). The review introduces the principle of corona discharge and describes the characteristics of plasma, especially of various corona plasma reactors. By summarizing the main features of such reactors, this paper provides a brief background to different power sources and reactor configurations and their application to VOC treatment design. Considering chlorinated compounds, benzene series and sulfur compounds, this paper reveals the probable mechanism of corona plasma in VOC degradation. Additionally, the effects of numerous technical parameters – such as reactor structure, shape and materials of electrodes, and humidity – are analyzed comprehensively. Product distribution, energy efficiency and economic benefits are invoked as factors to evaluate the performance of VOC degradation. Finally, the practical application of corona plasma and its advantages are briefly introduced. The review aims to illustrate the enormous potential of corona plasma technology in the treatment of VOCs, and identifies future directions.

Implications: This paper comprehensively describes the principle, characteristics, research progress and engineering application examples of the degradation of volatile organics by corona discharge plasma, to provide a theoretical basis for the industrial application of this process.     

Kinetics of Catalytic Oxidation of Benzene,n-Hexane,and Emission Gas from a Refinery Oil/Water Separator over a Chromium Oxide Catalyst

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.     

非热平衡等离子体协同催化脱除挥发性有机化合物的研究进展

单纯运用非热平衡等离子体(NTP)技术脱除挥发性有机化合物(VOCs)的效率和能量利用率并不高,而且在降解过程中可能会产生某些有害副产物。为了克服NTP技术在VOCs治理方面的缺陷,可将NTP和化学催化方法组合运用,结合两者的优势使系统的VOCs脱除率、能量利用率和CO2选择率显著提高。从催化反应器结构、NTP与催化剂协同作用的原理等方面总结了近年来NTP协同催化技术在VOCs脱除方面的应用状况。最后指出,NTP协同催化技术在VOCs脱除方面有良好的应用前景,但要真正实现其工程应用,仍有很多问题亟待研究和解决。     

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.     

Method for predicting photocatalytic oxidation rates of organic compounds

In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics.     

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.     

Careers in Air Pollution Control

Abstract

The destruction of parts per million (ppm) levels of volatile organic compounds in a dry air stream by high–energy electron–beam irradiation has been investigated in a pilot plant at the University of Tennessee Space Institute, Tullahoma, Tennessee. In a series of experiments, dry air contaminated with various VOCs in the concentration range of 50–1000 ppm were treated in the UTSI pilot plant to determine the extent of destruction at various electronbeam dose levels.

The destruction removal efficiency was determined as a function of the electron beam irradiation dose. The results suggest a charge transfer reaction as the major decomposition mechanism. A theoretical foundation of the process, along with a simple first–generation reaction kinetics model, a summary of the results from the pilot plant flow reactor, and a preliminary cost analysis for a fullscale detoxification plant using currently available electronbeam gun technology are presented in this paper.     

低温等离子体技术处理挥发性有机物

介绍了低温等离子体技术在处理挥发性有机物(VOCs)的研究现状和成果;探讨了低温等离子体技术的发展趋势.     

TiO2-assisted degradation of a perfluorinated surfactant in aqueous solutions treated by gliding arc discharge

The plasma–chemical degradation of Forafac 1110, a perfluorinated non-ionic surfactant, in aqueous solutions was investigated using TiO₂ catalysts. The considered plasma was the gliding arc in humid air, which results from an electric discharge at atmospheric pressure and quasi-ambient temperature. Two titanium dioxide powders were used and their synergistic effects on the Forafac degradation were compared. The results were discussed through the evolution of the pH, the conductivity, the fluoride ions concentration released in solutions, the surfactant concentration remaining after treatment and the chemical oxygen demand (COD) measurement.

The combination of the plasma–chemical treatment with heterogeneous catalysis through the use of TiO₂ accelerated the Forafac degradation, since only 60 min was sufficient to remove 96% instead of 360 min needed in the absence of TiO₂. The use of anatase and rutile under the trade-name of Rhodia TiO₂ and Merck TiO₂, respectively, led to different results, because Rhodia TiO₂ has proven to be more efficient. It would seem that the crystalline phase as well as the crystallite size, explain the efficiency of anatase. The advantage of the plasma-catalysis is due to the fact that there is a significant production of the OH^• radicals not only generated by the gliding arc discharge but also by TiO₂.     

活性炭吸附和脱附-等离子体氧化净化有机废气的研究

根据滑动弧放电等离子体适于降解高浓度有机物废气的特性,结合活性炭吸附法,提出了吸附器的吸附浓缩和热脱附-等离子体氧化净化有机废气的方法。在活性炭吸附过程中,最初2 h内甲苯净化率达到100%,随着时间的增加净化率下降;在热脱附滑动弧放电等离子体净化过程中,甲苯降解效率最高为97.3%。将滑动弧放电等离子体反应器出口气相产物收集进行FT-IR检测,发现放电后有CO2、CO、H2O和NO2产生,并分析了甲苯的降解机理。     

有机废气吸附净化处理的新型工艺研究

简要介绍了挥发性有机废气的来源、分类及其对人体和环境的危害，以及盐城市部分企业近年来的产生和排放状况。较详细地论述了吸附净化处理技术用于废气中挥发性有机化合物的去除和回收研究工艺与特点，阐明了目前有机废气的净化处理方向。     

Characterization of emissions during the heating of tyre contaminated scrap

In order to characterize the compounds (type and quantities) emitted during melting of organic contaminated scrap and to investigate the mechanism of their formation, an experimental set-up has been designed and built to study precisely the influence of temperature and gas atmosphere in the conditions of an electric arc furnace. These experiments lead to the determination of mass balances (C, H, O, S) and to the quantification of unburnt compounds (tars, carbon monoxide, volatile organic compounds (VOCs), benzene, toluene, ethylbenzene and xylenes (BTEX), polyaromatic compounds (PAHs)). Degradation conditions (gas atmosphere and temperature) corresponding to different areas in the electric furnace have also been investigated. Such experiments lead to a better understanding of degradation mechanisms; this interpretation is not possible from investigations performed in an industrial furnace since there are many uncontrolled parameters (large dispersion of the results).     

Analysis of VOCs in Ambient Air Using Multisorbent Packings for VOC Accumulation and Sample Drying

Abstract

Solid multisorbent packings have been characterized for trapping and release efficiency of trace (10-20 ppbv in humidified zero air) volatile organic compounds (VOCs). The use of a two-stage trapping system reduces sample water content typically by more than 95.5% while maintaining a trapping and release efficiency of 100% for 49 VOCs, including eight water-soluble VOCs. Three combinations of primary tube and focusing tube are examined in detail by using an atomic emission detector to monitor hydrogen as an indication of residual water vapor, and to monitor either chlorine, bromine, or carbon for target VOCs. Linearity of response to individual VOCs, the presence of artifacts, and a laboratory monitoring application are also discussed.     

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.     

Testing VOC emission measurement techniques in wood-coating industrial processes and developing a cost-effective measurement methodology

Availability of reliable emission measurements of concentrated volatile organic compounds (VOCs) bear great significance in facilitating the selection of a feasible emission abatement technique. There are numerous methods, which can be used to measure VOC emissions, however, there is no single method that would allow sampling of the whole range of volatile organics. In addition, research efforts are usually directed to the development of measuring VOCs in diluted concentrations. Therefore, there is a need for a novel measurement method, which can give reliable results while entailing simple operations and low costs. This paper represents a development effort of finding a reliable measurement procedure. A methodology is proposed and used to measure solvent emissions from coating processes.     

VOCs in representative canadian residences

Stored extracts of passive samplers exposed in 757 randomly selected Canadian residences provided a unique opportunity for retrospective determination of the occurrence of airborne volatile organic compounds (VOCs). Aliquots of the individual extracts were pooled to form a composite exposure sample and a corresponding blank sample. To identify and quantitate potentially hazardous organics in the samples, GC-MS analyses were conducted by several approaches. The amounts of 52 target compounds in the the composite sample were estimated based on selected ion monitoring (SIM) results, extraction recoveries, average air volume sampled, and 3M OVM 3500 passive sampling rates. Forty of the organics were detected and were present in amounts equivalent to airborne concentrations ranging from <1 to 104 μg m⁻³. Several other compounds were also tentatively identified by full scan analysis. Many of the detected organics have been reported to be associated with activities such as tobacco smoking and the presence of consumer products and plastic materials indoors. The analytical results have been useful in risk assessments and establishment of a new Canadian priority substances list (PSL).     

Microwave-induced combustion of volatile organic compounds in an industrial flue gas over the magnetite fixed-bed

A modified domestic microwave oven was applied to heat a magnetite (Fe₃O₄) fixed-bed for continuous decomposition of volatile organic compounds (VOCs), such as acetone, n-hexane, and dichloromethane (DCM), in a simulated flue gas which contains VOCs equivalent to 2000 ppmv as DCM. Experimental results revealed that effect of the addition of water to the inlet stream on decomposition of DCM in the overall experiment was insignificant. Bulk temperature of the Fe₃O₄ fixed-bed was also found to reach 600 °C from an initial room temperature by 6.5 min under microwave radiation, even though the inlet gas was at a high gas hourly space velocity of 5240 h⁻¹ and a high relative humidity of 75%. Moreover, the VOCs in the inlet stream could be decomposed completely over the Fe₃O₄ fixed-bed by microwave heating at a power level of 645 W at heating time of 10 min. The conversion of VOCs is stable when the Fe₃O₄ fixed-bed has been heated longer than 10 min with microwave radiation. The microwave-induced heating upon Fe₃O₄ fixed-bed processing appears to be not only an energy efficient technique for air pollutions treatment but also a promising technology for variety of VOCs in a flue gas from industrial factory being decomposed simultaneously and completely.     

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.     

Economic Study of the Tunable Electron Beam Plasma Reactor for Volatile Organic Compound Treatment

ABSTRACT

A tunable electron beam generated plasma system has been developed for selective cold plasma treatment of dilute concentrations (1-3,000 ppm range) of hazardous compounds in gaseous waste treatment. This system, referred to as the Tunable Hybrid Plasma (THP), has shown a high degree of efficiency and effectiveness in both laboratory and field tests. Decomposition energy requirements are in the 100 eV per molecule range for treatment of carbon tetrachloride and 10 eV for treatment of trichloroethylene.

A cost comparison has been made between the Tunable Hybrid Plasma (THP) technology and three conventional technologies used for emission control of volatile organic compounds (VOCs): granular activated carbon, thermal incineration, and catalytic oxidation. In addition to its environmentally attractive features, THP technology has the potential to be lower cost than other technologies over a range of concentrations and flow rates. Cost projections for the THP system for decomposition of trichloroet-hylene are around 50 cents/lb for initial concentrations in the few hundred ppm range and flow rates of 5,000 cfm or greater and around $1/lb for 1,000 cfm flow rates. Cost projections for carbon tetrachloride and trichloroethane decomposition using the THP technology are several dollars per pound. The costs for THP treatment are generally significantly lower than costs for use of granular activated carbon and are also quite competitive with costs for thermal incineration and catalytic oxidation.     

Photocatalytic decomposition on nano-TiO₂: destruction of chloroaromatic compounds

Photocatalysis is applied increasingly in addressing and solving environmental and energy-related problems. Especially the TiO₂-derived catalysts attract attention because of their catalytic efficiency, wide range of applications, ease in use, and low cost (it costs about 150 Yuan a kilogram in China). This review first describes the principles of photocatalytic destruction by semiconductors and then focuses on degradation rates and reaction mechanisms in a variety of photocatalytic uses of modified TiO₂. Finally, these concepts are illustrated by selected examples relating to the photocatalytic degradation of organic persistent pollutants, such as polychlorinated benzenes (PCBz), biphenyls (PCB) and dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). And some approaches towards industrial application are analyzed.