Journal of Electrostatics 55 (2002) 189201

Effects of adsorption and temperature on a nonthermal plasma process for removing VOCs
Young-Hoon Songa,*, Seock-Joon Kima, Kyung-Il Choib, Toshiaki Yamamotoc
a b

Korea Institute of Machinery and Materials, 171 Jang-Dong, Yusung-gu, Taejon, South Korea SK Daeduk Institute of Technology, 140-1 Wonchon-Dong, Yusung-gu, Taejon, South Korea c Department of Energy Systems Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, 599-8531 Osaka, Japan

Received 24 December 1999; received in revised form 5 June 2001; accepted 7 October 2001

Abstract Simultaneous use of nonthermal plasma and adsorption process for removing volatile organic compounds (VOCs) has been investigated. Toluene (C7H8) and propane (C3H8), which have different adsorption behavior, were treated using three different types of the barrier discharge reactors packed with glass, macro-porous g-Al2O3, or molecular sieve 5A pellets mixed with the g-Al2O3 beads, respectively. Test results show that the removal rates of the VOCs treated by nonthermal plasma process increase with the assistance of adsorption. The enhanced removal rates with the adsorption process are maintained under increased temperature conditions, although the adsorption capability is apparently decreased as the temperature increases. In addition, O3 and HNO3 generated from the nonthermal plasma process are signicantly decreased with g-Al2O3 beads, which is another technical advantage to use g-Al2O3 beads. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nonthermal plasma; Adsorption; VOCs; Molecular sieves

1. Introduction Removal process of volatile organic compounds (VOCs) with nonthermal plasma is of interest not only in scientic elds but also in the industrial elds in which applications of conventional techniques for VOCs removal process have been limited. For example, incineration technique might not be appropriate in the case of
*Corresponding author. 0304-3886/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 8 6 ( 0 1 ) 0 0 1 9 7 - 8

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low concentrations of VOCs, typically lower than 1000 ppm, since the technique inherently needs to increase the enthalpy of the rest of the gas molecules that consist of more than 99.9% of the treated gas [1,2]. Catalytic technique could use less heat energy compared with the incineration technique, since the technique can selectively oxidize VOCs. However, even this technique has limited applications when the heat energy to activate the catalysts is not available. One example is the cold start of lean burn gasoline engines in which 7080% of unburned hydrocarbons are emitted during the initial 60100 s. Nonthermal plasma process, which can work without heat energy, has a high potential in such industrial processes in which the use of heat is not convenient. To date, feasibility of the nonthermal plasma process for treating VOCs has been evaluated in numerous industrial processes, such as cold start of engine [3], semiconductor process [4], a large facility for treating VOCs [1], etc. Two important issues of nonthermal plasma process for removing VOCs are (1) reducing power consumption and (2) treatments of inorganic and organic by-products emitted from the process. Various approaches have been suggested to overcome these two problems [510], and increasing the residence time of VOCs in the plasma reactor is one of the methods to reduce the operating power [5]. Recently, as a practical approach to increase the residence time without increasing the size of the reactor, a macro-porous g-Al2O3 or molecular sieve hybrid reactor, which adsorbs VOCs selectively, has been suggested by Ogata et al. [6,7]. They reported that the emission of CO and N2O from the process could be decreased with the g-Al2O3 or molecular sieve hybrid reactor and the energy efcient removal process can be obtained [6,7]. Considering the importance of adsorption in the catalytic process and the feasibility of nonthermal plasma process assisted by catalytic technique [6,7,9,11,12], previous investigations of the nonthermal plasma process with adsorption process are in the early stages. For example, each previous study was conducted with limited types of VOCs, adsorbents, temperature, ow conditions, and geometrical congurations of the reactors. Theoretical and empirical data is not yet sufcient for engineering design of a nonthermal plasma process assisted by catalytic technique. The present study investigated the effects of adsorption and temperature on the nonthermal plasma process to remove toluene and propane as an effort to extend the present understanding of the nonthermal plasma process with adsorption process. gAl2O3 or molecular sieve 5A beads have been used in the present study while adsorbing materials are packed into the nonthermal plasma reactor. The results of these tests with adsorption process were compared with the test results with glass beads that have no capability for adsorption. Electrical parameters of the reactors were investigated along with the behaviors of the adsorption, desorption, and oxidation process, since the characteristics of electrical discharge and adsorption can be simultaneously varied depending on the materials packed into the reactors. Finally, the process temperature has been controlled up to 1001C in the present tests in order to characterize the temperature effects on the adsorption and oxidation process.

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2. Experimental approach Fig. 1 shows the experimental apparatus used in the present study. The treated gases are supplied from a compressor, and are heated by an electrical heater for temperature control. The air supplied into the reactor has 18% relative humidity. The reactor is located in the electrically heated oven to maintain a constant temperature. In this way, the temperature conditions were controlled from room temperature to 3001C. The ow rate of the treated gases is kept at 10 l/min during the whole test. A bubbling cylinder and an ice bath are used to steadily supply toluene into the reactors. A gas cylinder is used to supply propane. The packed-bed reactor consists of an emitting wire, a pyrex tube wrapped by a thin copper sheet, and small-sized beads. The diameter of the pyrex tube is 30 mm, and the length of the tube is 300 mm. The types of the beads packed into the reactor are glass, g-Al2O3 (Procatalyse Co., model: A.A. 2-5 Grade P), or molecular sieve 5A (Aldrich), respectively. g-Al2O3 has 330 m2/g of surface area and macro-porosity ( (>70 A), where molecular sieve 5A has a higher value (560 m2/g) of surface area and ( micro-porosity (o5 A). Both materials are able to enhance the amount of adsorption of various types of hydrocarbons due to high surface area and small pore structure. The diameters of beads are ranged from 2 to 5 mm with 3 mm of mean diameter. The AC power supply used with the packed-bed reactor generates up to 20 kV of the peak voltage, and 60 Hz of the xed frequency. The voltage and current at the reactors were measured with a digital oscilloscope (Tektronix TDS 754C) in which the power consumption at the reactor was calculated by the integration of the voltage and current. The analog power meter (Yokogawa) measured the power consumption of the AC power supply. Fig. 2(a) shows the oscillograms of the voltage, current, instant power, and time-integrated

Bead Glass Tube (Barrier) Oven

High-Voltage AC Power Supply

Insulation Compressor MFC Silica gel MFC M FC Ice water Needle Valve Outer Electrode (Ground) Center Electrode Outlet injection Heater

Outlet (Vent) Inlet injection

Sampling FTIR

Vent

Air

Toluene Bubbling

Ice bath

Hydro Carbon

Fig. 1. Schematic of experimental apparatus.

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Fig. 2. (a) Oscillograms of voltage, current, power, and time-integrated power with the glass bead reactor (carrier gas: air 10 l/min, room temperature condition). (b) Typical Q2V plot for estimating the capacitance of the glass bead reactor.

instant power measured at the reactor packed with the glass beads. For these measurements, 10 l/min of air was supplied into the reactor at room temperature. Fig. 2(b) shows a VoltageCharge Lissajous gure (Q2V plot) to characterize the electrical discharge of the reactor. Due to the scattered data points on this plot, the estimated values of the discharge power based on the plot do not show consistency. The multiplication of the scattered data of the voltages and capacitance has inherently resulted in such erroneous estimation. Here, the formula for the discharge power can be expressed as P 4fCD 1=1 b Vonset Vpeak Vonset ; where P is the power consumption at the reactor, f the frequency, CD the capacitance of dielectric, Cg the capacitance of gas, b Cg =CD ; Vonset the voltage at charge Q 0; and Vpeak the peak applied voltage [13]. The capacitance and onset voltages obtained directly from the plot can be used only for the purpose of qualitative comparison to understand the electrical characteristics of the reactors packed with different types of beads, as listed in Table 1. Typical values to characterize the electrical discharge in three different packed-bed reactors are listed in Table 1. Here, the g-alumina/molecular sieve 5A reactor means that the packed materials in the reactor are evenly mixed with g-alumina beads and the molecular sieve 5A pellets. The same applied voltage based on the read-out on the power supply, i.e. 19 kV, was applied for these measurements. In Table 1, Vrms and Irms stand for the rms values of the voltages and currents, and Pmean is the averaged value of the time-integrated instant power consumption at the reactor obtained from the digital oscilloscope. Pwall is the power consumption at the power supply and is measured both with the oscilloscope and the analog power meter. As

Y.-H. Song et al. / Journal of Electrostatics 55 (2002) 189201 Table 1 Electrical characterstics of the reactors at room temperature condition Vrms (kV) Glass bead reactor g-alumina reactor g-alumina/MS 5A reactor
a

193

Irms (mA) 1.05 1.80 1.60

Pmean (W) 10.5 18.5 15.0

Pwall (W) 50 53 52

CD (pF)a 620 680 676

Vonset (kV)a 15.6 13.0 13.7

17.8 18.0 17.5

Obtained based on Q2V plots.

shown in Table 1, the power consumption at the glass bead reactor is the smallest among the reactors used in the study. The power consumption of the power supply does not signicantly change under the present test conditions. In later sections, the performance of each reactor while removing VOCs is evaluated based on the power consumption at the reactors. Qualitative comparisons of the electrical discharge in three different types of the reactors were made with CD and the Vonset obtained from the Q2V plots. Among the reactors used in the study, as shown in Table 1, the glass bead reactor has the smallest capacitance, and the highest onset voltage, which results in the smallest power consumption. In addition, about 10% of power consumption at the reactors was transiently varied while treating toluene and propane gases. Since the temperature and water concentrations change along with time due to dielectric heating and the adsorption and desorption process, such variations of the electrical power was inevitable under the present test conditions. Under one specic test condition, the voltages indicated on the read-out of the power supply were adjusted in the range of 1970.5 kV to maintain the constant power consumption at the reactors.

3. Results and discussion Fig. 3 shows the adsorption, desorption, and removal process of toluene with the nonthermal reactor packed with the g-Al2O3 beads. The test was conducted under room temperature (251C) condition. The outlet concentrations of toluene, CO2, and H2O were simultaneously measured with FTIR (model: Bio-Rad FTS 3000) that has capability of on-line measurements of organic and inorganic chemicals. In the rst 150 min, the toluene concentrations measured at the outlet of the reactor were lower than the inlet concentration, 220 ppm, due to strong adsorption of toluene. In addition, CO2 and H2O were also adsorbed during this early period. After the outlet concentrations of toluene reached the inlet concentration, 19 kV of AC power was applied to start the nonthermal plasma process. Immediately after the plasma process started, desorption of toluene, CO2, and H2O were observed, which lasted for 25 min. After this desorption period, the outlet concentrations of toluene and

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300 700 600 500 C7 H8 CO2 H2 O 3000 Plasma on 250 2500 200
H2O (Relative)

C7H8 [ppm]

2000 400 1500 300 1000 200 100 0 0 20 40 60 80 100 120 140 160 180 200 220 injection 500 50
CO2 [ppm]

150

100

Time [min]

Fig. 3. Concentrations of toluene, CO2, and H2O along with time. Flow rates, 10 l/min; temperature, 251C; Pmean ; 18.5 W; Pwall ; 50 W; applied voltage; 19 kV on the power supply.

CO2 approach the steady values. Since a preliminary test result conrms that CO2 cannot be strongly adsorbed on the g-Al2O3 beads, most of the amounts of CO2 emitted from the reactor are produced through the oxidation of toluene. In this test procedure, as discussed in Section 2, characteristics of electrical discharge changed with time. Decreasing currents and increasing voltages are especially noticeable in the initial period and then these variations gradually diminished after this period. In this early stage, H2O was also actively desorbed from the reactor, as shown in Fig. 3, which might be one of the reasons for such variations. During the test, the voltage ranging from 18.5 to 19.5 kV on the read-out of the power supply was adjusted to maintain the constant power consumption. During the toluene desorption period shown in Fig. 3, the desorption peaks of CO2 and H2O, which are the nal products of the oxidation process, were also observed. This observation implies that the most active oxidation process occurred simultaneously with the toluene desorption process. The amount of desorbed toluene is equivalent to one-third of the amount of the adsorbed toluene in the early 150 min, which indicates that two-thirds of the amount of the toluene adsorbed in the early 150 min is oxidized during the next 25 min of desorption period. Therefore, the largest amount of toluene is oxidized during this period without further electrical power consumption at the reactor and at the power supply. This observation supports the statement, concluded by Ogata et al. [6], that an energy efcient technique to oxidize the adsorbed VOCs can be utilized when adsorption and nonthermal plasma discharge process are operated at an optimized interval. The feasibility of the adsorption process in a plasma reactor, especially in the initial period of the electrical discharge is discussed above. As a next step, the effects of the adsorption on the steady state removal process were investigated. Here, the

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steady state removal process is the period when the outlet concentration of toluene drops to a steady state value, as shown in Fig. 3. Removal rates, which are dened as the ratio of the removed concentrations to the inlet concentrations, were compared. Fig. 4 shows two different removal process of toluene with the g-Al2O3 bead rector or the glass bead reactor. As shown in Fig. 4, a strong adsorption process appears with the g-Al2O3 bead rector. For the case of the glass bead reactor, the variations of the outlet concentrations respond in a short time along with the operating conditions, such as hydrocarbon injection and onset of the electrical discharge. During the steady state removal process, the removal rates with the g-Al2O3 and glass bead rectors are 77% and 42%, respectively. The test results in Fig. 4, unfortunately, are not conclusive to show the benecial effects of adsorption on the steady state removal process. Although the g-Al2O3 bead rector showed a signicantly higher removal rate, the enhanced removal rate might have resulted not only from adsorption but also from the increased power consumption at the reactor. As listed in Table 1, the power consumption at the g-Al2O3 bead rector is also higher than the glass bead reactor. In order to clarify the favorable effects of adsorption, the comparison tests were conducted with another type of reactor that has stronger adsorbents but has similar power consumption with the g-Al2O3 bead rector. In this new type of reactor, equal amounts of g-Al2O3 beads and molecular sieve 5A pellets were packed. As shown in Table 1, the power consumption at the new reactor is smaller than that of the g-Al2O3 bead rector, but

600

Al2O3 packed Glass bead packed. inlet injection Room Temp. Plasma on

600

500

500

C7H8, [ppm]

400

400

300

300

200

200

100

injection

100

0 -150 -100 -50 0 50

Time [min]
Fig. 4. Removal process of toluene with g-Al2O3 or glass bead reactors. Flow rates, 10 l/min; temperature, 251C; mean power, 10.5 W (glass bead), 18.5 W (g-Al2O3); applied voltage, 19 kV on the power supply.

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this discrepancy is reduced compared with the previous comparison test between the glass and g-Al2O3 bead reactors. In addition, the treated gas is changed from toluene to propane, since the removal rates of toluene with the g-Al2O3 bead rector under the present test condition is already too high to compare. Fig. 5 shows the removal process of propane with the g-Al2O3 or glass bead reactors, respectively. As shown in Fig. 5, the removal process of propane with the g-Al2O3 bead reactor and the glass bead reactor are very similar. The concentrations of propane measured at the outlet of the g-Al2O3 bead reactor reached the inlet concentration in a short time, which indicated that propane is not adsorbed into the g-Al2O3 beads. The removal rates of propane with the g-Al2O3 bead reactor are not signicantly increased, although the delivered power to the g-Al2O3 bead reactor is higher than that to the glass bead reactor by a factor of two. This lower enhancement of the propane removal rate implies that the higher power consumption with the g-Al2O3 bead reactor might not be an exclusive reason for the high removal rate of toluene in the g-Al2O3 bead reactor, shown in Fig. 4. Fig. 6 shows the removal process of propane with the g-Al2O3/molecular sieve 5A bead reactor. Molecular sieve 5A has a higher surface area and a much smaller pore ( size (o5 A) compared to the g-Al2O3, which results in propane adsorption appeared in Fig. 6. The removal rate of propane during the steady removal process reaches 85%. This removal rate with the molecular sieve is signicantly higher than the cases of the glass bead (17%) or the g-Al2O3 bead (23%) reactors that do not have a strong

250

C3H8

250

200

200

C3H8 [ppm]

150 Glass bead - Al 2O3 100 Plasma on

150

100

50 injection 0 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80

50

Time [min]
Fig. 5. Removal process of C3H8 with g-Al2O3 or glass bead reactors. Flow rates, 10 l/min; temperature, 251C; mean power, 10.5 W (glass bead), 18.5 W (g-Al2O3); applied voltage, 19 kV on the power supply.

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360 340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 0 20 40 60 80 100 300 Plasma on 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 120 140 160 180 200 C3H8 CO2

197

Time (min)

Fig. 6. Adsorption, desorption, and removal process of propane packed with 50% of zeolite and 50% of g-Al2O3 pellets. Flow rates, 10 l/min; temperature, 251C; Pmean ; 15 W.

capability of adsorption of propane. The present test results with the molecular sieve can be applied to develop a technique to reduce the power consumption in treating VOCs, since the enhanced removal process with the molecular sieve was obtained with the smaller electrical power consumption compared with the g-Al2O3 bead reactor. With the present scope of the tests, clarifying every reason for the improved removal process is not easy because of the various aspects of chemical reactions and electrical discharge. The present test results, however, clearly show that the electrical power needed for removing VOCs can be reduced with adsorption process not only in the initial periods of electrical discharge but also in the steady state removal process. The above observation of the improved performance with the adsorption process can be explained in two ways. First, due to additional adsorption and desorption procedure, residence time in the reaction zone is increased; therefore, higher conversion can be achieved. Second, the g-Al2O3 and molecular sieve 5A are hydrophilic materials, in other words, a lot of hydroxyl group exists on the surface of the catalyst. They can be converted into OH radical by nonthermal plasma process. As a result, higher performance of oxidation can be observed. The later proposal is being identied indirectly by a study of NOx removal process with and without g-Al2O3, which is conducted in one of the authors laboratory. A preliminary test result shows that the oxidation of NO2 by OH radicals can be enhanced with g-Al2O3.

Carbondioxide Conc. (ppm)

Propane Conc. (ppm)

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Hsiao et al. demonstrated that nonthermal plasma process removes VOCs more effectively as the process temperature increases [14]. They tested this result with a pulsed corona reactor and explained their results with the increased kinetic reaction rates of O radicals at elevated temperature conditions. However, regardless of such favorable effects of the elevated temperature condition, one cannot say that the removal process with adsorption would be improved as the temperature increases, since the increased temperature condition can adversely affect the performance of the adsorption process. The process temperature was increased up to 1001C to investigate the favorable and unfavorable effects of temperature on the process. Fig. 7 shows the removal process of toluene with the g-Al2O3 bead and the glass bead reactor under the elevated temperature condition. The carrier gases and reactors in the oven are electrically heated at 1001C. The concentrations of toluene at the inlet section of the reactors are 254 ppm for the g-Al2O3 bead reactor and 200 ppm for the glass bead reactor, respectively. As shown in Fig. 7, 40 min were taken to reach the inlet concentration in the case of the g-Al2O3 reactor. This time period for the adsorption process at the elevated temperature is signicantly reduced, compared to the case at room temperature. However, regardless of the reduced capability of the adsorption process at the elevated temperature condition, the removal rates of the toluene with the g-Al2O3 reactor are higher than those with the glass reactor. In addition, the removal rates at the elevated temperature are better than those at room temperature. The present results showed that the favorable effects of the elevated temperature condition for removing toluene were more

400 350 glass reactor power on -Al2O3 reactor power on -Al2O3 test glass test

400 350 300 250 200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

toluene concentration [ppm]

300 250 200 150 100 50 0

time [min]
Fig. 7. Adsorption, desorption, and removal process of toluene in the g-Al2O3 bead reactor at 1001C.

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dominant compared with the unfavorable effects caused by the reduced adsorption capability. To this point, enhanced removal process assisted by the adsorption has been discussed. In addition to this technical advantage, the use of g-Al2O3 beads in the nonthermal plasma process lead to practical merit, i.e. reduction of some of the gas phase by-products generated by the nonthermal plasma process. Fig. 8 shows FTIR

Fig. 8. FTIR spectrum of the glass and g-Al2O3 bead reactors. Process temperature, 1001C; toluene in air is treated.

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spectrum of the emitted gases from the outlet of the g-Al2O3 and the glass bead reactors at 1001C. In the gures, some peaks are identied and some are not yet identied. The calibrated gases (C7H8, NO, NO2, CO, CO2) or vaporized nitric acid (HNO3) were fed into the reactor to identify the spectrum peaks of the FTIR. As shown in the gure, some of the gas phase by-products, e.g. O3 and HNO3, emitted from the g-Al2O3 bead reactor, are predominantly small, compared with those from the glass bead reactor. The peaks of NO2, however, appear to be increased in the case of the g-Al2O3 bead reactor, which indicated that reaction pathways in the plasma reactor could be modied by the presence of the g-Al2O3 beads.

4. Conclusion Adsorption, desorption, and oxidation process of toluene and propane with the g-Al2O3, glass, and molecular sieve 5A bead reactors have been investigated at room and elevated temperature conditions. Strong adsorption behavior and enhanced removal efciencies are observed when the tested hydrocarbons are treated with the g-Al2O3 or molecular sieve 5A beads. The present test results indicate that increased residence time due to selective adsorption of VOCs results in such enhanced removal efciencies. At the elevated temperature condition, adsorption capability of g-Al2O3 decreases compared with the room temperature condition. However, the removal rate of the g-Al2O3 bead reactor is still higher than that of the glass beads despite the losing adsorption capability due to the elevated temperature condition. In addition, analysis of the FTIR spectrum indicates that the use of the g-Al2O3 beads is crucial to reduce some of the by-products, such as O3 and HNO3.

Acknowledgements This work was partially supported by the Ministry of Science and Technology of Korea and G7 Next Generation Vehicle Program.

References
[1] R.G. McInnes, Explore new options for hazardous air pollutant control, Chem. Eng. Prog. (1995) 3648. [2] H.R. Paur, Removal of volatile hydrocarbons from industrial off-gas, in: B.M. Penetrante, S.E. Schultheis (Eds.), Non-thermal Plasma Techniques for Pollution Control, Part B, Springer, Berlin, 1993, pp. 7789. [3] G. Lepperhoff, K. Hentschel, P. Wolters, W. Neff, K. Pochner, F.-J. Trompeter, Lean-combustion spark-ignition engine exhaust aftertreatment using non-thermal plasma, SAE 982512. [4] D. Evans, J.J. Coogan, G.K. Anderson, L.A. Rosocha, M.J. Kushner, Plasma remediation of trichloro-ethylene in silent discharge plasmas, J. Appl. Phys. 74 (9) (1993) 53785386. [5] T. Yamamoto, VOC decomposition by nonthermal plasma processingFa new approach, J. Electrostat. 42 (1997) 227238.

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[6] A. Ogata, K. Yamanouchi, K. Mizuno, S. Kushiyama, T. Yamamoto, Oxidation of dilute benzene in an alumina hybrid plasma reactor at atmospheric pressure, Plasma Chem. Plasma Processing 19 (3) (1999) 383394. [7] A. Ogata, D. Ito, K. Mizuno, S. Kushiyama, T. Yamamoto, Removal of dilute benzene using zeolitehybrid plasma process, Proceedings of the 1999 IEEE-IAS Conference, Phoenix, AZ, 37 October, 1999, pp. 14831488. [8] T. Oda, T. Takahashi, K. Tada, Decomposition of dilute trichloroethylene by nonthermal plasma, IEEE Trans. Ind. Appl. 35 (2) (1999) 373379. [9] T. Yamamoto, K. Mizuno, I. Tamori, A. Ogata, M. Nifuku, M. Michalska, G. Prieto, Catalysisassisted plasma technology for carbon tetrachloride destruction, IEEE Trans. Ind. Appl. 32 (1) (1996) 100105. [10] M.C. Hsiao, B.T. Merrit, B.M. Penetrante, G.E. Vogtlin, P.H. Wallman, Plasma assisted decomposition of methanol and trichloroetylen in atmospheric pressure air streams by electrical discharge processing, J. Appl. Phys. 78 (5) (1995) 293299. [11] A. Mizuno, A. Chakrabariti, Okazaki, Application of corona technology in the reduction of greenhouse gases and other gaseous pollutants, in: B.M. Penetrante, S.E. Schultheis (Eds.), Nonthermal Plasma Techniques for Pollution Control, Part B, Springer, Berlin, 1993, pp. 165184. [12] H.H. Kim, S. Katsumura, A. Mizuno, NOx control using combination process of photocatalyst and discharge plasma, Proceedings of the Second International Symposium on Non-thermal Plasma Technology for Gaseous Pollution Control, Salvador, Brazil, August, 1997. [13] U. Kogelschatz, Advanced ozone generation, in: S. Stucki (Ed.), Process Technologies for Water Treatment, Plenum Press, New York, 1988, pp. 87120. [14] M.C. Hsiao, B.M. Penetrante, B.T. Merrit, G.E. Vogtlin, P.H. Wallman, Effect of gas temperature on pulsed corona discharge processing of acetone, benzene, ethylene, J. Adv. Oxid. Technol. 2 (2) (1997) 306311.