Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004, pp.

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Improvement of Ozone Yield by a Multi-Discharge Type Ozonizer Using Superposition of Silent Discharge Plasma
Hyun-Jig Song
Department of Computer Applied Electricity, Gumi College, Gumi 730-711

Byung-Joon Chun and Kwang-Sik Lee

School of Electrical Engineering & Computer Science, Yeungnam University, Gyungsan 712-749 (Received 2 September 2003, in nal form 9 April 2004) In order to improve ozone generation, we experimentally investigated the silent discharge plasma and ozone generation characteristics of a multi-discharge type ozonizer. Ozone in a multi-discharge type ozonizer is generated by superposition of a silent discharge plasma, which is simultaneously generated in separated discharge spaces. A multi-discharge type ozonizer is composed of three dierent kinds of superposed silent discharge type ozonizers, depending on the method of applying power to each electrode. We observed that the discharge period of the current pulse for a multidischarge type ozonizer can be longer than that of silent discharge type ozonizer with two electrodes and one gap. Hence, ozone generation is improved up to 17185 ppm and 783 g/kwh in the case of the superposed silent discharge type ozonizer for which an AC high voltages with a 180 phase dierence were applied to the internal electrode and the external electrode, respectively, with the central electrode being grounded.
PACS numbers: 52 Keywords: Environmental Applications

I. INTRODUCTION

Ozone has been used widely for the treatment of water and exhausted smoke, deodorization, color removal, disinfection, etc. because of its strong oxidation. It is well known that the high-pressure barrier discharge plasma (the so-called silent discharge plasma) has become one of the powerful methods for ozone production since the pioneering work by Siemens [1,2]. Most technical silent discharge type ozonizers use a pair of electrodes. Silent discharge type ozonizers consist of a narrow discharge space, formed between a dielectric and a high voltage electrode, and ground electrode outside of the dielectric. The process gas, usually air or oxygen, is passed through a narrow annular discharge gap, and through the plasma chemistry of a micro-discharges, it is partially converted into ozone. In a silent discharge plasma, a micro-discharge will be started by completion of a Townsend discharge for a small nd (n: particle density of the ozonizer; d: gap space), a high (Townsend coecient which describes the number of secondary electrons released from the cathode), and a slowly varying eld. For a large nd, a low , and a rapidly varying eld (using pulsed ozonizers), a micro-discharge is initiated
E-mail:

hjsong@kumi.ac.kr

by a streamer that produces enough charge and induces distortion at its head to achieve breakdown in a single transit [3, 4]. Charge is accumulated in the area where micro-discharges reach the dielectric when the current is initiated in micro-discharges. In sequence, the electric eld in the gap is weak. When the eld is weak, attachment becomes more important than ionization and detachment. The micro-discharge is interrupted before leader formation or spark discharge. Since the process gas in the discharge column is not heated up, current ow stops below the breakdown eld. The next microdischarge at the same position can occur only after the eld has been raised again to fulll the initiation condition. In the mean time, micro-discharges will strike at other positions of the dielectric. By repetition of these sequences, micro-discharges are initiated and choked [5, 6]. In the silent discharge type ozonizer broad application of ozone is known to be hindered primarily because of its low ozone yield. The 1200 g/kwh theoretical ozone yield is calculated by using thermo-chemical theory [7]. In a practical ozonizer, the discharge energy is dissipated not only in producing ozone but also in heating the electrodes of the ozonizer and the test gas. Then the produced ozone is also destroyed by heat. So far, there have been many attempts to improve the eciency of ozone generation for industrial uses of such discharges [810]. The eciency depends on the gas pres-

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sure, temperature, and humidity as well as the discharge conditions such as the gap width, the electrode surface, and the electrode material including dielectric [1113]. In ozone generation, the superposition eect of two types of discharges in the same discharge space, silent and surface discharges, is reported [14]. Their ozonizer has two power sources with a variable-phase shifter. About a 20 30 % increase in the eciency is observed in their ozonizer [15]. In this study, a new multi-discharge type ozonizer with two spaces and three electrodes for improvement of the ozone yield is experimentally proposed to investigate the discharge and the ozone generation characteristics of a superposition silent discharge plasma. Depending on the power supply used for each electrode, the multi-discharge type ozonizer was composed of three kinds of superposed silent discharge type ozonizers, which are IESDO, CESDO and CISDO. IESDO is a superposed silent discharge type ozonizer for which the AC high voltages applied to the internal electrode and the external electrode have a 180 phase dierence and for which the central electrode is grounded. CESDO is a superposed silent discharge type ozonizer for which the AC high voltages applied to central electrode and the external electrode have a 180 phase dierence and for which the internal electrode is grounded. CISDO is a superposed silent discharge type ozonizer for which AC high voltages applied to the central electrode and the internal electrode have a 180 phase dierence and for which the external electrode is grounded. For superposed silent discharge type ozonizer, the characteristics of the discharge voltage and current waveforms were analyzed at a discharge power of 8 W and supplied oxygen gas ow rate of 2 /min. For various quantities of supplied oxygen gas, the ozone concentration and yield were investigated as a function of the number of a superposed silent discharge type ozonizers. The ozone generation yield was estimated as a function of the rate of supplied oxygen gas for each superposed silent discharge type ozonizer. The environmental application of a multi-discharge type ozonizer for dyeing wastewater was also investigated.

Fig. 1. Schematic diagram of the multi-discharge type ozonizer with a coaxial double cylindrical system.

II. EXPERIMENTAL APPARATUS AND METHODS Figure 1 shows a schematic diagram of a multidischarge type ozonizer with a coaxial double cylindrical system. A multi-discharge type ozonizer consists of three electrodes (central electrode, internal electrode and external electrode), two dielectrics (int glass and Pyrex glass), and two gap spaces (the discharge space between central electrode and the internal electrode, and the discharge space between the internal electrode and the external electrode). The central electrode was made with a low pressure glow discharge plasma lamp that installed a cone ferrite

oxide electrode inside cylindrical int glass tube with a thickness of 1.0 mm and an outside diameter of 12 mm. The internal electrode was manufactured with stainless steel mesh 0.035 mm thick and 130 mm long, that turns around the central electrode, keeping the gap between the central electrode and the inner discharge space at 0.4 mm. The external electrode was a 1.0 mm thick copper coil wrapped around the outside surface of Pyrex glass in 5 mm interval to a length of 130 mm, keeping the space between the internal electrode and the outer discharge space at 1.9 mm. One of the three electrodes was grounded, and AC high voltage, with a 180 phase dierence, were applied to the other two electrodes. Therefore, multi-discharge type ozonizers form three dierent kinds of superposed silent discharge type ozonizers with dierent discharge and ozone generation characteristics. At this time, overlapping silent discharge plasmas, produced individually in the inner discharge space and the outer discharge space, generate ozone for each superposed discharge type ozonizer. Figure 2 presents a schematic diagram of the experimental setup. The dotted line shows the ow of supplied oxygen gas and ozonized gas, and the solid line is the connecting circuit line for the power source and the measurement apparatus. The applied high voltage was displayed from the AC power source of each superposed silent discharge type ozonizer, and when the supplied oxygen gas (temperature 25 C, purity 99.99 %) owed into the superposition discharge type ozonizer, it was controlled by using a ow meter. The discharge power was measured with a digital power meter (Light Star, DPM 20, Korea) at the input terminal of the AC power source. This included discharge power of the superposed silent discharge ozonizer, the high voltage transformer loss, and the power line loss.

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Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004

Fig. 2. Schematic diagram of the experimental setup consisting of a multi-discharge type ozonizer using superposition of a silent discharge plasma.

The discharge voltage, current, and waveform were measured with a digital storage oscilloscope (Lecroy Model 9350AL, USA), a high voltage divider (Pulse Electronics Model EP-50K 2000:1, Japan), and a 50 non-inductive resistor at a supplied oxygen gas 2 /min and a discharge power of 8 W. Also, these values were displayed using a PC and were printed. Next, the ozone concentration of the multi-discharge type ozonizer was measured with an ozone monitor (Okitronics Ltd. OZM-7000G, Japan) when the number of each superposed silent discharge ozonizer was one or three. The ozone yield was calculated by using the ozone concentration and the discharge power. For three superposed discharge type ozonizers, the ozone characteristics were measured and calculated by using a series connection in the ow path of the supplied oxygen gas. In order to research the dependence of the ozone generation characteristics on the shape of the superposed silent discharge type ozonizer, we compared the ozone yield rates for IESDO, CESDO, and CISDO.

Fig. 3. Discharge voltage and current waveforms at a discharge power of 8 W and a supplied oxygen gas ow of 2 /min for each superposed discharge type ozonizer.

III. EXPERIMENTAL RESULTS AND DISCUSSION

Figure 3 shows the discharge voltage and current waveforms at a discharge power of 8 W and a supplied oxygen gas ow rate of 2 /min for IESDO, CESDO, and CISDO. The discharge voltage waveforms of CH1 and CH2 were distorted 60 Hz sinusoidal waves with a 180 phase dierence. The discharge value of CH2 was higher than that of CH1 because the outer discharge space, 1.9 mm, was wider than the inner discharge space, 0.4 mm. The current pulse CH3 was generated in the inner discharge space and the outer discharge gap space until the peak voltage reached the maximum voltage point of the

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Fig. 4. Photographs of the discharge phenomena at a discharge power of 8 W and a supplied oxygen gas ow of 2 /min for each superposed discharge type ozonizer.

AC high voltages of CH1 and CH2 with a 180 phase difference. The discharge of a multi-discharge type ozonizer could be sustained much longer than that of a silent discharge type ozonizer due to the interactions of the silent discharge plasma that occurred in each discharge space. The current pulse of a multi-discharge type ozonizer formed two times for one cycle in each discharge space by overlapping the silent discharge plasma produced in each discharge space because the discharge period occurs four times. Figure 4 displays photographs of the discharge phenomena in IESDO, CESDO, and CISDO at a discharge power of 8 W and a supplied oxygen gas ow rate of 2 /min. The silent discharge plasma in the 0.4 mm inner discharge space for CISDO and the silent discharge plasma in the 1.9 mm outer discharge space for IESDO contribute greatly to ozone generation. The ozone characteristics of a multi-discharge type ozonizer were improved compared to those of a silent discharge type ozonizer by superposing silent discharge plasmas that occur in the inner discharge space and the outer discharge space, which achieves the carrier role of a discharge. Figure 5 shows ozone concentration and yield characteristics with variation of quantity of supplied oxygen gas at discharge power each 8 W and 24 W when number of IESDO, CESDO and CISDO are one and three. The ozone concentration is proportional to operating number of superposed discharge type ozonizers, but inversely proportional to the rate of supplied oxygen gas. The maximum values of the ozone concentration in Figure 5(a), (b) and (c) were, respectively, 17185 ppm, 8606 ppm, and 5407 ppm when the operating number of superposed discharge type ozonizer was three and the oxygen gas was supplied at a rate of 2 /min.

Fig. 5. Ozone concentration and yield as functions of the rate of supplied oxygen gas at discharge powers of 8 W and 24 W when number of each SDO is one and three.

As the rate of supplied oxygen gas was decreased, the time that oxygen molecules stay in discharge area was prolonged, and ozone generation reactions occurred vigorously: O2 + e 2O + e O + O2 O3 O2 + e O + e 2 O 2 +eO+O+e (1) (2) (3) (4)

where e, O, O2 and O3 are electrons, oxygen atoms, oxygen molecules in the ground state, and ozone, respectively. The collision probability of oxygen molecules and

-1186Table 1. Passing time, T , of the discharge space and passing time, t, of the spiral of the external electrode. Rate of supplied oxygen gas [ /min] 2 4 8 12 16 T [ms] 448.0 224.0 112.0 75.0 56.0 t [ms] 18.0 9.0 4.5 3.0 2.3

Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004

electrons was increased due to reiteration of the silent discharge plasma that occurred from the inner discharge space and the outer discharge spacer of each superposed discharge type ozonizer. The oxygen gas passing time, T , of the discharge space (length 130 mm, volume 13432 mm3 ) and the passing time, t, of the oxygen in a spiral type external electrode are shown in Table 1 for various supplied oxygen gas ow rates, the ozone concentration is proportional to T and t. In Figure 5, the maximum ozone yield for one operating superposed discharge type ozonizer was obtained at a supplied oxygen gas ow rate of 4 /min, and the maximum ozone yields for three superposed discharge type ozonizers, operated simultaneously, were obtained at supplied oxygen gas ow rates of 16 /min, 12 /min, and 8 /min, respectively. The maximum values of the ozone yield in Figure 5(a), (b) and (c) were, respectively, 783 g/kwh, 246 g/kwh, and 120 g/kwh for three operating superposed discharge type ozonizers. In the Figure 5, IESDO has almost 4 times the production rate in comparison with the other cases. The discharge spaces of IESDO and CESDO are much wider than that of CISDO, but the ground electrode area of IESDO is much larger than that of CESDO. Also, the discharge between CE-IE and the discharge between CE-EE are superposed in the discharge space in case of IESDO. These result in an activation of the silent discharge and improve the ozone concentration and yield. The ozone yield, given by the product of the discharge power by the ozone generation amount, depends on the amount of ozone generated when the discharge power is xed. The maximum ozone generation occurred when the decrement of the ozone concentration and the increment in the quantity of ozone generation were equal to each other. In this point of view, rate of supplied oxygen gas at which maximum ozone generation was increased with increasing ozone concentration because decrease ratio in the quantity of ozone generation decreased with increasing rate of supplied gas [1618]. As shown in Figure 5(a), (b), and (c), when the number of operating superposed discharge type ozonizer was one, the maximum ozone yield was obtained when the oxygen gas was supplied at a rate of 4 /min because the

Fig. 6. Ozone yield rate, , as a function of the rate of supplied oxygen gas with the superposed discharge type ozonizer parameter.

ozone concentration was low. However, when the number of operating superposed discharge type ozonizer was three, the maximum ozone yield was obtained at a rate of supplied oxygen gas of 16 /min because the ozone concentration with IESDO was high. When the oxygen gas was supplied at a rate lower than 4 /min for three operating ozonizers, the ozone yield was low compared to that for one operating ozonizer. This results from ozone concentration, space density augmentation, and ozone dissociation reactions such as O + O3 2O2 O3 + e O2 + O + e (5) (6)

Figure 6 shows the ozone yield rate, , as a function of the rate of supplied oxygen gas for the three kinds of superposed discharge type ozonizers. At this time, ozone yield rate, was compared with ozone yield of IESDO and CESDO about ozone yield of CISDO. When the number of operating superposed discharge type ozonizers was one or three, was classied as 1 or 3 , respectively. The values of the ozone yield rates for the three kins of a superposed discharge type ozonizer occurred in the order ESDO > CESDO > CISDO. The silent discharge

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the silent discharge, ozone generation, and the environment improvement characteristics as functions of the rate of supplied oxygen gas, as well as the form and the number of operating superposed discharge type ozonizer. The following results were obtained: 1. Among the three electrodes that make up the multi-discharge type ozonizer, AC high voltages with a 180 phase dierence were applied to two electrodes and the other electrode was grounded. The three kinds of superposed discharge type ozonizers had dierent discharge and ozone generation characteristics.
Fig. 7. Absorption characteristics of an organic compound in the visible region for various contact times, , of ozone and dyeing wastewater.

2. The multi-discharge type ozonizer had improved ozone generation characteristics compared to the silent discharge type ozonizer due to reiteration of the silent discharge plasma that occurred in two discharge spaces. 3. Among the three kinds of superposed discharge type ozonizers, IESDO had excellent ozone generation characteristics. 4. The ozone concentration of the multi-discharge type ozonizer was proportional to the number of operating superposed discharge type ozonizers and inversely proportional to the rate of supplied oxygen gas. Also, the ozone yield of the multidischarge type ozonizer was proportional to the number of operating superposed discharge type ozonizers and the rate of supplied oxygen gas.

Fig. 8. Photographs of the dyeing wastewater when is 1 min and 30 min, respectively. (a) = 1 min, (b) = 30 min

5. The maximum values of the ozone concentration and yield of the multi-discharge type ozonizer were 17185 ppm and 783 g/kwh, respectively. 6. When dyeing wastewater was reacted with 17185 ppm ozone, it become almost white after 30 min. Therefore, these results show that this ozonizer can be applied to water treatment systems for environment improvement.

plasma eects on ozone generation was largest for the IESDO with a big outer discharge gap space. Figures 7 and 8 depict the decolorization eect of wastewater by using IESDO. Figure 7 shows the absorption characteristics of an organic compound in the wavelength region of visible light (400 700 nm) for various contact times of ozone and dyeing wastewater, , for an ozone concentration of 17185 ppm produced from IESDO in dyeing wastewater. Figure 8 shows photographs of a dyeing wastewater when is 1 min and 30 min, respectively. The adsorption decreases as is prolonged, and dyeing wastewater that is yellowish brown becomes white. Therefore, a multi-discharge type ozonizer can be used for water environment improvement.

REFERENCES
[1] A. Vosmaer, Ozone (Van Nostrand, New York, 1916). [2] B. Eliasson and U. Kogeischatz, J. Appl. Phys. 20, 1421 (1987). [3] B. Eliasson and U. Kogeischatz, IEEE Trans on PS 19, 309 (1991). [4] W. Egli and B. Eliasson, Helvetica Phys. Acta. 62, 302 (1989). [5] M. B. Chang, Ozone Science and Engineering 19, 241 (1997). [6] J. S. Chang and K. Ichikawa, Polish J. Appl. Chem. 39, 611 (1995). [7] J. S. Chang, P. A. Lawless and T. Yamamoto, IEEE Trans on PS 19, 1152 (1991).

IV. CONCLUSIONS A new multi-discharge type ozonizer, utilizing a superposition of a silent discharge plasma with two discharge spaces and three electrodes, is proposed to investigate

-1188[8] Takchiko Sato, Hideya Nishiyama and Makato Kambe, J. Korean Phys. Soc. 42, 782 (2003). [9] Youngho Kim, Min Suk Cha, Wan-Ho Shin and YoungHoon Song, J. Korean Phys. Soc. 43, 732 (2003). [10] S. Masuda, K. Akutsu and M. Kuroda, IEEE Trans on IA 24, 223 (1988). [11] J. D. Moon, S. T. Geum, G. T. Lee and D. K. Park, J. Korean Phys. Soc. 38, 680 (2001). [12] J. M. Lim, B. Y. Jeon and C. M. Lee, J. Korean Phys. Soc. 37, 1051 (2000). [13] W. J. M. Samaranayake, Y. Miyahara and T. Namihira,

Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004 IEEE Trans on EI 7, 254 (2000). [14] C. Yamabe, S. Takase and M. Hayashi, in Proceeding 2nd International Symposium High Pressure Low Temperature Chemistry (Kazimierz, Poland, 1989), p. 39-44. [15] T. Ito and Y. Ehara, Trans on IEE 112A, 41 (1992) (in Japanese). [16] H. J. Song and K. S. Lee, Trans on KIEE 48, 533 (1999). [17] H. J. Song and K. S. Lee, Trans on KIIEE 13, 109 (1999). [18] H. J. Song and K. S. Lee, Trans on KIIEE 15, 25 (2001).