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SwRI Technology Today - "Harmful Compounds Yield to Nonthermal Plasma Reactor"

Harmful Compounds Yield to Nonthermal Plasma Reactor
New gaseous emissions abatement method can be tailored to treat specific industrial effluents by Michael G. Grothaus, Ph.D., and E. Robert Fanick

E. Robert Fanick (left) is a senior research scientist specializing in diesel emissions characterization in the Department of Emissions Research, Automotive Products and Emissions Research Division. Dr. Michael Grothaus, a senior research engineer in the Communications Engineering Department, Automation and Data Systems Division, studies advanced applications of high-power electromagnetic systems. The pulsed corona reactor (PCR) in the foreground was constructed as part of an SwRI internal research program to demonstrate an innovative method for the removal of harmful compounds from gaseous wastestreams using nonthermal plasmas.

It is well known that airborne emissions from the manufacturing, transportation, and utility industries can contribute to ozone-induced smog and acid rain, as well as potential global warming and atmospheric ozone depletion mechanisms. Increasingly stringent environmental regulations and policies intended to reduce air pollution have necessitated the development of alternative abatement methods for a wide variety of harmful gaseous compounds. An industry's failure to comply with the provisions and amendments of the Clean Air Act of 1990, the Federal Facilities Compliance Act, and other state, federal, and international air standards can result in costly fines and interruption of operations. Compounds subject to regulation include volatile organic compounds (VOC) such as toluene and methylene chloride, perfluorinated compounds (PFC) such as nitrogen trifluoride and sulfur hexafluoride, oxides of nitrogen (NOx) and sulphur (SOx), and particulate matter (PM).

A nonthermal plasma is a partially ionized gas in which the mean energy of the electrons is considerably higher than that of the ions and bulk-gas molecules. The electric discharge-based nonthermal plasma shown here was created in a cylindrical reactor. The discharge is formed through the application of an intense electric field, which causes the formation of a multitude of self-propagating electron avalanches (known as streamers) within the gas volume.

In the microelectronics industry, for example, PFCs are used extensively for such processes as plasma enhanced chemical vapor deposition, plasma etching, and plasma cleaning. Applications such as semiconductor wafer cleaning and oxidation enhancement employ a wide variety of VOCs, many of which have been identified as ozone depleters or associated with potential global warming mechanisms.[1]
www.swri.org/3pubs/ttoday/spring96/ttoday2.htm 1/7

consider that 39 percent of NOx released into the atmosphere originates from mobile sources. because engine modifications designed to reduce NOx emissions usually result in increased particulate emissions. Called the pulsed corona reactor (PCR). making the precise chemical composition of a wastestream difficult to characterize. or able to destroy multiple pollutant compounds. in which the entire wastestream is elevated to a high temperature to treat a dilute pollutant concentration (typically a few hundred parts per million).swri. but rather a complex mixture of compounds. the high operating temperatures subject surrounding structures to thermal stress. dry. A pulsed corona discharge is created by applying a series of fastrising. more stringent regulations and operational requirements. those covering NOx and particulate emissions from diesel engines are among the most sweeping. for instance. achieving the zero emissions goal sought by the microelectronics industry probably will require continued use of some form of aftertreatment. is routinely employed in semiconductor fabrication and other manufacturing facilities.org/3pubs/ttoday/spring96/ttoday2."Harmful Compounds Yield to Nonthermal Plasma Reactor" In general. is desired. Thermal incineration entails mixing the process exhaust with hydrogen or oxygen and then passing the mixture through an ignitor where the effluent gases burn. and subatmospheric plasma. The pulses are formed by charging an energy storage capacitor (milliseconds) www. While the ideal solution to this problem would be to develop cleaner processing methods. Wet reactors operate by passing the exhaust gas through an absorbing spray of water or other chemicals. only a small portion of harmful gases is consumed during semiconductor fabrication. which can lead to exhaustive equipment maintenance schedules and the generation of unwanted reaction by-products. In collaboration with industry and the military. or to recover and recycle unused process chemicals. and vice versa. wet. As another example. Southwest Research Institute (SwRI) engineers are developing a new technology that transforms environmentally harmful air pollutants into less harmful constituents. This type of reactor is the final stage of an overall hazardous gas abatement system at many industrial facilities. as is eventual disposal of pollutant-saturated liquids. wet. Conventional Air Pollution Treatment Options Conventional emissions control methods rely on four different technologies: thermal. This technique. a semiconductor manufacturing facility may employ thermal. engineering trade-offs may make further simultaneous reductions of NOx and particulates impractical. Thus. Each approach has distinct advantages but also suffers from serious limitations in light of new. adding to operating costs. the amount of oxygen or hydrogen added is usually substantial.[4] Two or more of these techniques are sometimes combined in a treatment scheme. process energy goes not only into destroying unwanted compounds.htm 2/7 . Limited solubility of some pollutants in the scrubbing liquid is a concern. Faced with this challenge. Also. the technology consists of a nonthermal plasma reaction process under atmospheric pressure. Therefore.[3] Tests conducted at SwRI have shown that the PCR has the potential to neutralize a wide variety of pollutants in an energy-efficient manner. and subatmospheric plasma methods to achieve high levels of pollutant destruction. The effective destruction of harmful gases is further complicated by the fact that such emissions are not composed of a single pollutant compound entrained in a simple background gas.28/01/13 mechanisms. engine manufacturers are considering novel forms of exhaust aftertreatment to meet tougher engine emissions standards. so the effluent stream from a particular process may contain relatively large quantities of toxic and environmentally harmful compounds.[2] Of the many environmental laws in force. In addition to these energy-efficiency concerns.[1] SwRI Technology Today . high-voltage pulses to a field-enhanced geometry such as the coaxial wire-cylinder configuration shown here. Although significant emissions reductions have been achieved through improved engine design and electronic control. a treatment option that is highly generic. but also into heating the vastly more abundant background gas.

Inc. A combination of thermal and dry techniques can be found in a catalyst bed. In addition. while higher temperatures cause the pollutant to decompose and react with the granules. Plasma -. exhaust gases from the process chamber pass through a nonthermal plasma. formed by the high energy electrons contained within the discharge can then preferentially react with the pollutant molecules. The following describes the operational theories and characteristics of nonthermal plasma reactors. Catalysts beds are widely used in industry.600 K). enough energy is introduced so the plasma constituents are in thermal equilibrium -. While under vacuum. Because the electrons are preferentially excited in a nonthermal plasma.the ions and electrons are. however. Applying these pulses generates filamentary corona discharges that are distributed down the length of the central wire. as well as the results of tests conducted during a project involving the Institute's Automation and Data Systems Division and Automotive Products and Emissions Research Division. This nonthermal condition can be created at both atmospheric and subatmospheric pressures. on average.1-10 Torr) plasma reactors are used to destroy hazardous gaseous compounds emanating from industrial facilities requiring vacuum conditions to maintain cleanliness and precise process control. www. Chemically active species. their effectiveness tends to be limited to a single pollutant compound. at the same temperature. they are susceptible to poisoning. or temperature. Depending on the amount of energy added. This energy-savings potential is a primary reason why nonthermal technologies are being investigated at SwRI.htm 3/7 . or radicals. but high volume throughput. The temperature of thermal plasma components is about 1-2 electron-volts (1 eV is associated with 11. Included in this discussion is a unique application of the technology that has proven capable of simultaneously removing NOx and PM in diesel exhaust emissions. and therefore high treatment rates.28/01/13 SwRI Technology Today ."Harmful Compounds Yield to Nonthermal Plasma Reactor" formed by charging an energy storage capacitor (milliseconds) and then quickly releasing this energy to the reactor through a fast switch (nanoseconds) such as a high-pressure hydrogen spark gap. A nonthermal plasma is one in which the mean electron energy. a condition in which undesired variables cause the reaction to cease prematurely.the Fourth State of Matter A plasma can be described as a gas to which a specific amount of energy has been added to separate the gas component molecules into a collection of ions. The room temperature condition results in chemisorption. can only occur at atmospheric pressures. A disadvantage of this technique is that solidphase by-products can accumulate on the reactor's internal surfaces or back-diffuse toward the processing reactor. and other species in varying degrees of excitation. In dry reactors. where they are broken down. An electrical arc is one example of a thermal plasma. while the background gas remains at ambient temperature. In a thermal plasma. which is used to lower overall activation energy for the chemical reaction of interest. charge-neutral gas molecules. leaving the more massive ions with lower energy. electrons. Subatmospheric (0. the resulting plasma can be characterized as thermal or nonthermal.swri. converting them to less hazardous or more easily handled compounds. causing damage to the pumping mechanism. they are inherently non-generic. corrupting the operating environment. Because energy is added to the electrons instead of the ions and background gas molecules. nonthermal plasma reaction.org/3pubs/ttoday/spring96/ttoday2. An innovative alternative to existing techniques that promises to be both highly generic and energyefficient is a method based on an atmospheric pressure. a significant energy savings can be realized. the exhaust gases pass through a bed of granules held at either room temperature or above. a familiar manifestation of which is a lightning bolt bridging the gap between a storm cloud and the earth. the electrons can attain energies of from 1-10 eV. or be swept from the reactor into the vacuum pump. is considerably higher than that of the bulk-gas molecules. and researchers from the Naval Surface Warfare Center and Air Products and Chemicals.

Not only must the window be thin enough to allow the accelerated electrons to penetrate into the reaction chamber.28/01/13 SwRI Technology Today . in turn. reactions normally constrained to occur at high temperatures are now possible at essentially room temperatures. As in a catalyst. electrons are created and then accelerated to high energies under vacuum conditions in a vessel outside the intended reaction chamber. creating chemically active species known as radicals. The radicals can preferentially react with pollutant molecules in the gas stream.htm In cooperation with the Naval Surface Warfare Center and Air Products and Chemicals. the greater the volume of gas that can be treated per unit of time. A representative chemical reaction in a PCR is illustrated in the sidebar titled. the plasma electrons collide with the background gas molecules. self-propagating electron avalanches. the more streamers per unit length are produced.[5] In an electron-beam system. Generating Nonthermal Plasmas Techniques employed in the generation of atmospheric-pressure.[6] Discharge-based systems have the advantage of producing high-energy electrons directly within the treated gas volume through the application of locally intense electric fields. The PCR is a discharge-based device in which a series of high-voltage pulses is applied to a thin metal wire located coaxially within a metal tube. breaking them down into less hazardous or more easily handled compounds. this requires pulses with risetimes of a few nanoseconds (ns) and pulsewidths of less than 100 ns. Once created. For most geometries. Recently. can collide with molecules in the background gas. SwRI researchers investigated the PCR as an abatement technique for the treatment of semiconductor 4/7 . called streamers or coronas. the higher the pulse repetition frequency. such as H2 and O2. can be formed within the gas volume. freeing more electrons in the process.org/3pubs/ttoday/spring96/ttoday2. The faster the pulse. Destruction efficiency can be enhanced by the addition of small amounts of reagent gases. As an added complication. The width of the applied electrical pulses is minimized to prevent undesirable streamer thermalization. Similarly. their electrical and physical performance remains to be verified. to the wastestream. streamers must be terminated quickly through external or self-quenching mechanisms before the much heavier ions left behind in the streamer channel gain enough energy from the imposed electric field to transition to the arc or thermal plasma condition. Applying pulses to this geometry generates a number of streamers within the gas volume that emanate from the wire to the cylinder. Once generated. and then introduced into the reaction chamber through a thin metal or semiconducting window. nonthermal plasmas can be categorized as either electron-beam or electrical discharge-based." Semiconductor Industry Emissions www. In this way. The level of destruction possible for a given compound depends on the precise composition of the background gas. causing a plasma to form. ultra-thin semiconductor windows have been developed that may reduce the required acceleration voltage to 75 kV or less. The plasma chemistry can be tailored for specific industrial effluents. " Plasma Chemistry in the Pulsed Corona Reactor.swri."Harmful Compounds Yield to Nonthermal Plasma Reactor" The PCR technique has been evaluated for removal of several hazardous compounds under a variety of operating conditions. an acceleration voltage of more than 150 kV can be required. The electrons bombard the background gas. Electrons created in or entering these regions can be accelerated to high energies and. however. To effectively penetrate conventional metal-foil windows. but it must also be robust enough to maintain the vacuum/atmospheric interface and withstand the physical stresses created by heat resulting from the beam. which requires appropriate shielding. The principal problem with this approach is development of a suitable window. electrons of this energy can lead to the formation of X-rays.

pollutant concentrations of a few hundred ppm. the chemical content of the post-reactor 5/7 . Extensive. Eighty five percent of the CCl2F2 was destroyed. and CH3CCl3. with destruction levels exceeding 99. dichlorodifluoromethane (CCl2F2).[7] The reactor used in these tests consisted of 10 one-inch diameter. The chemical and electrical performance of the PCR was analyzed for the following pollutant compounds: toluene (C7H8).9 percent destruction figure indicates that the detection limits of the gas chromatograph or mass spectrometer (MS) were surpassed. hexafluoroethane (C2F6). manipulation of additive concentrations. For www. The risetime of the pulses was 6 ns.1-trichloroethane (CH3CCl3). threefoot long reaction chambers operating in parallel."Harmful Compounds Yield to Nonthermal Plasma Reactor" Identifying reaction by-products is central to the evaluation of new hazardous gas abatement methods. methylene chloride (CH2Cl2). as well as NF3. and with hydrogen or oxygen as additives (a few hundred ppm). Remarkable levels of destruction also were obtained for the extremely stable PFC molecules: 32 percent in the case of C2F6 (with 50 percent O2) and CF4 (with 8 percent O2). with an overall pulsewidth of less than 100 ns. the next logical step was to identify the reaction by-products. CH2Cl2. nitrogen trifluoride (NF3).htm each process gas of interest. as illustrated in the figure previously shown. Further improvement of nonthermal chemical destruction efficiencies is being pursued through variation of the additive species. For example.28/01/13 researchers investigated the PCR as an abatement technique for the treatment of semiconductor processing tool effluent. diesel exhaust is essentially a lean air mixture. Effluent containing a dilute concentration of NF3 in a nitrogen background with a hydrogen additive was processed by a PCR and analyzed by mass spectrometry. The VOCs C7H8. whereas the effluent from a semiconductor fabrication facility is primarily nitrogen. Typical energy densities applied to the reactor were less than 1. Results showed a marked decrease in pollutant concentration and an increase in the by-products F2 and HF. are water-soluble.000 Joules/liter (the energy density applied to the gaseous wastestream for a particular destruction efficiency forms a basis of comparison with other nonthermal plasma reaction schemes). Stable operation of the reactor was demonstrated at voltages up to 35. carbon tetrafluoride (CF4). the use of a hydrogen additive dramatically improved the destruction efficiency attainable for NF3 by allowing the dissociated fluorine atoms to be removed in the form of hydrofluoric acid (HF).000 V and repetition rates to 1.swri. Thermal methods require a substantially higher energy expenditure to achieve similar chemical destruction efficiencies. fast electrical diagnostics were used to accurately determine the electrical efficiency of the reactor. Furthermore. unlike NF3. With the reactor bounded by 100-300 watts of input power. For instance. and 72 percent in the case of SF6. Although some applications specifically require the exclusive use of ambient air. 1. SwRI Technology Today . significant removal levels of certain VOCs and PFCs were achieved. and optimization of PCR electrical operating parameters.org/3pubs/ttoday/spring96/ttoday2.9 percent. were effectively removed from the gas stream. many industrial processes are not so constrained. Having shown significant removal for the compounds of interest.500 pulses per second (Hz). Additives such as hydrogen or oxygen can act as recombination sites for dissociated components of the pollutant compound. which. The background gas containing the pollutant to be destroyed plays a significant role in that destruction.1. The greater than 99. the addition of small concentrations of certain reagent gases to the process stream was found to be beneficial in enhancing the destruction efficiencies of some compounds. process-stream flow rates of 5-10 liters per minute in air or nitrogen. and sulfur hexafluoride (SF6).

The scans were compared to identify the components showing the most significant change.28/01/13 SwRI Technology Today . The figure at left above shows the results of a dynamic scan of the principal by-products. Consortium tests are being conducted in an SwRI diesel engine test stand.9] The packed-bed reactor contains a multitude of dielectric pellets contained between a set of high-voltage electrodes. the decrease in NF3 concentration shows up as a corresponding increase in the concentration of HF and F2. Static. and these were subsequently monitored during an MS dynamic scan. For each process gas of interest. The original pollutant compound. Both HF and F2 are water soluble and therefore easily removed by a wet reactor. For the compounds of interest to the semiconductor industry. or time-integrated. NF3. and subsequently neutralized or recycled. could not have been removed by conventional techniques without expending significant amounts of energy. has been investigated at SwRI as a means of obtaining simultaneous particulate and NOx reduction in diesel engine exhaust. The reactor operates on essentially the same principles as the PCR. obtained during destruction of NF3 in a background of nitrogen containing a hydrogen additive.an older www. scans were taken of the background gas. the packed-bed reactor. specifically NOx. the chemical content of the post-reactor effluent was determined by taking a series of MS scans.[8. Another type of nonthermal plasma reactor. the background gas with the PCR running. the background gas plus pollutant and/or additive. the full process gas stream with the PCR running. The Institute has assembled a consortium of diesel engine and equipment manufacturers to evaluate the viability of nonthermal plasma techniques for the simultaneous removal of NOx and particulate emissions from mobile sources.swri. Diesel Exhaust NOx/Particulate Removal No single commercially available aftertreatment technique for diesel exhaust has the combined effect of reducing particulate emissions while also affecting gaseous emissions. with the PCR running and idle. and. HF and fluorine gas (F2). the reaction by-products identified to this point appear to be easily removed with a simple wet reactor.htm 6/7 .org/3pubs/ttoday/spring96/ttoday2. finally. The performance of a reactor bed provided by AEA Technology in Great Britain was evaluated on two different light-duty diesel vehicles representing two different engine technologies -. As shown. except the streamer discharges take place in the gaseous voids existing between individual pellets. which measured compound concentration over time."Harmful Compounds Yield to Nonthermal Plasma Reactor" the reaction by-products.

maintainability. Published in the Spring 1996 issue of Technology Today®. with the CO concentration falling off at higher space velocities.an older indirect-injection Toyota truck and a newer direct-injection Dodge truck. published by Southwest Research Institute.org/3pubs/ttoday/spring96/ttoday2.28/01/13 SwRI Technology two different light-duty diesel vehicles Today . a consortium of diesel engine and equipment manufacturers has been formed to further investigate various methods of nonthermal plasma generation for the reduction of NOx and particulate emissions. The results showed that simultaneous removal of NOx and PM in diesel exhaust is indeed possible with a dischargebased plasma reactor. Conclusions Although the underlying concept of nonthermal plasma destruction of a wide variety of pollutant molecules has been demonstrated. although the efficacy of the technique predictably declines at higher flow rates for a given device geometry.swri. The performance of the reactor was also evaluated over a light-duty transient cycle with similar results. identification of all reaction byproducts. Exhaust flow rates from 1-7 liters/ minute through a small-scale reactor were examined to determine the effect of gas flow rate on the operation of the plasma aftertreatment system. and demonstration of the devices' reliability. Because concentrations of CO in diesel exhaust are typically low. For more information. contact Joe Fohn. An increase in carbon monoxide (CO) was detected at the reactor exit. establishing the viability of the nonthermal plasma approach will require not only examination of its chemical efficiency under a wide variety of conditions. and scalability. this level of undesired by-product may be acceptable. In view of these concerns. but also measurement of electrical efficiency and prime power requirements."Harmful Compounds Yield to Nonthermal Plasma Reactor" representing two different engine technologies -.htm 7/7 . The most promising devices will undergo additional development and testing to determine the practical limits and operating characteristics of these devices in a realistic diesel exhaust aftertreatment scenario. A similar approach is being pursued to determine the impact of nonthermal plasma systems on multiconstituent semiconductor processing tool effluent. Spring 1996 Technology Today SwRI Publications SwRI Home www.