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

1182∼1188

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 final 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
different 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 multi-
discharge 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
difference 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 by a streamer that produces enough charge and induces

Ozone has been used widely for the treatment of water
and exhausted smoke, deodorization, color removal, dis-
infection, 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 dis-
charge 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 den-
sity of the ozonizer; d: gap space), a high Γ (Townsend
coefficient which describes the number of secondary elec-
trons released from the cathode), and a slowly varying
field. For a large nd, a low Γ, and a rapidly varying field
(using pulsed ozonizers), a micro-discharge is initiated
∗ E-mail: hjsong@kumi.ac.kr
-1182-
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
field in the gap is weak. When the field is weak, at-
tachment 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
flow stops below the breakdown field. The next micro-
discharge at the same position can occur only after the
field has been raised again to fulfill the initiation condi-
tion. 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 applica-
tion 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 elec-
trodes of the ozonizer and the test gas. Then the pro-
duced ozone is also destroyed by heat.
So far, there have been many attempts to improve the
efficiency of ozone generation for industrial uses of such
discharges [8–10]. The efficiency depends on the gas pres-
Improvement of Ozone Yield by a Multi-Discharge Type Ozonizer· · · – Hyun-Jig Song et al.
sure, temperature, and humidity as well as the discharge
conditions such as the gap width, the electrode surface,
and the electrode material including dielectric [11–13].
In ozone generation, the superposition effect of two types
of discharges in the same discharge space, silent and sur-
face discharges, is reported [14]. Their ozonizer has two
power sources with a variable-phase shifter. About a
20 ∼ 30 % increase in the efficiency 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 super-
posed silent discharge type ozonizers, which are IESDO,
CESDO and CISDO. IESDO is a superposed silent dis-
charge type ozonizer for which the AC high voltages ap-
plied to the internal electrode and the external electrode
have a 180◦ phase difference 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 difference and for which the internal
electrode is grounded. CISDO is a superposed silent dis-
charge type ozonizer for which AC high voltages applied
to the central electrode and the internal electrode have
a 180◦ phase difference and for which the external elec-
trode 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 flow rate of 2 `/min. For
various quantities of supplied oxygen gas, the ozone con-
centration 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 ap-
plication of a multi-discharge type ozonizer for dyeing
wastewater was also investigated.
II. EXPERIMENTAL APPARATUS AND
METHODS
Figure 1 shows a schematic diagram of a multi-
discharge type ozonizer with a coaxial double cylindrical
system. A multi-discharge type ozonizer consists of three
electrodes (central electrode, internal electrode and ex-
ternal electrode), two dielectrics (flint glass and Pyrex
glass), and two gap spaces (the discharge space between
central electrode and the internal electrode, and the dis-
charge space between the internal electrode and the ex-
ternal electrode).
The central electrode was made with a low pressure
glow discharge plasma lamp that installed a cone ferrite
-1183-
Fig. 1. Schematic diagram of the multi-discharge type
ozonizer with a coaxial double cylindrical system.
oxide electrode inside cylindrical flint 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
difference, were applied to the other two electrodes.
Therefore, multi-discharge type ozonizers form three
different kinds of superposed silent discharge type ozoniz-
ers with different discharge and ozone generation charac-
teristics. At this time, overlapping silent discharge plas-
mas, 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 exper-
imental setup. The dotted line shows the flow of sup-
plied 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 (tempera-
ture 25 ◦ C, purity 99.99 %) flowed into the superposition
discharge type ozonizer, it was controlled by using a flow
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 dis-
charge power of the superposed silent discharge ozonizer,
the high voltage transformer loss, and the power line loss.
-1184- Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004

Fig. 2. Schematic diagram of the experimental setup con-

sisting of a multi-discharge type ozonizer using superposition
of a silent discharge plasma.

The discharge voltage, current, and waveform were mea-

sured with a digital storage oscilloscope (Lecroy Model
9350AL, USA), a high voltage divider (Pulse Electronics
Model EP-50K 2000:1, Japan), and a 50 Ω 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 (Ok-
itronics Ltd. OZM-7000G, Japan) when the number
Fig. 3. Discharge voltage and current waveforms at a dis-
of each superposed silent discharge ozonizer was one or
charge power of 8 W and a supplied oxygen gas flow of 2
three. The ozone yield was calculated by using the ozone `/min for each superposed discharge type ozonizer.
concentration and the discharge power. For three super-
posed discharge type ozonizers, the ozone characteristics
were measured and calculated by using a series connec-
tion in the flow path of the supplied oxygen gas. In or- Figure 3 shows the discharge voltage and current wave-
der to research the dependence of the ozone generation forms at a discharge power of 8 W and a supplied oxy-
characteristics on the shape of the superposed silent dis- gen gas flow rate of 2 `/min for IESDO, CESDO, and
charge type ozonizer, we compared the ozone yield rates CISDO. The discharge voltage waveforms of CH1 and
for IESDO, CESDO, and CISDO. CH2 were distorted 60 Hz sinusoidal waves with a 180◦
phase difference. 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 dis-
III. EXPERIMENTAL RESULTS AND charge space and the outer discharge gap space until the
DISCUSSION peak voltage reached the maximum voltage point of the
Improvement of Ozone Yield by a Multi-Discharge Type Ozonizer· · · – Hyun-Jig Song et al. -1185-

Fig. 4. Photographs of the discharge phenomena at a dis-

charge power of 8 W and a supplied oxygen gas flow of 2
`/min for each superposed discharge type ozonizer.

AC high voltages of CH1 and CH2 with a 180◦ phase dif-

ference. The discharge of a multi-discharge type ozonizer
could be sustained much longer than that of a silent dis-
charge 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 phe-
nomena in IESDO, CESDO, and CISDO at a discharge
power of 8 W and a supplied oxygen gas flow rate of 2
`/min.
The silent discharge plasma in the 0.4 mm inner dis-
charge space for CISDO and the silent discharge plasma
in the 1.9 mm outer discharge space for IESDO con-
tribute greatly to ozone generation.
Fig. 5. Ozone concentration and yield as functions of the
The ozone characteristics of a multi-discharge type
rate of supplied oxygen gas at discharge powers of 8 W and
ozonizer were improved compared to those of a silent 24 W when number of each SDO is one and three.
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 As the rate of supplied oxygen gas was decreased, the
a discharge. time that oxygen molecules stay in discharge area was
Figure 5 shows ozone concentration and yield charac- prolonged, and ozone generation reactions occurred vig-
teristics with variation of quantity of supplied oxygen gas orously:
at discharge power each 8 W and 24 W when number of
O2 + e → 2O + e (1)
IESDO, CESDO and CISDO are one and three.
The ozone concentration is proportional to operating O + O2 → O3 (2)
number of superposed discharge type ozonizers, but in-
versely proportional to the rate of supplied oxygen gas. O2 + e → O∗2 + e (3)
The maximum values of the ozone concentration in Fig- O∗2 +e→O+O+e (4)
ure 5(a), (b) and (c) were, respectively, 17185 ppm, 8606
ppm, and 5407 ppm when the operating number of super- where e, O, O2 and O3 are electrons, oxygen atoms, oxy-
posed discharge type ozonizer was three and the oxygen gen molecules in the ground state, and ozone, respec-
gas was supplied at a rate of 2 `/min. tively. The collision probability of oxygen molecules and
-1186- Journal of the Korean Physical Society, Vol. 44, No. 5, May 2004

Table 1. Passing time, T , of the discharge space and pass-

ing time, t, of the spiral of the external electrode.

Rate of supplied
T [ms] t [ms]
oxygen gas [`/min]
2 448.0 18.0
4 224.0 9.0
8 112.0 4.5
12 75.0 3.0
16 56.0 2.3

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 flow
rates, the ozone concentration is proportional to T and
t.
In Figure 5, the maximum ozone yield for one oper-
ating superposed discharge type ozonizer was obtained
at a supplied oxygen gas flow rate of 4 `/min, and the
maximum ozone yields for three superposed discharge
type ozonizers, operated simultaneously, were obtained
at supplied oxygen gas flow rates of 16 `/min, 12 `/min,
and 8 `/min, respectively. Fig. 6. Ozone yield rate, η, as a function of the rate of sup-
The maximum values of the ozone yield in Figure 5(a), plied oxygen gas with the superposed discharge type ozonizer
(b) and (c) were, respectively, 783 g/kwh, 246 g/kwh, parameter.
and 120 g/kwh for three operating superposed discharge
type ozonizers.
In the Figure 5, IESDO has almost 4 times the pro- ozone concentration was low. However, when the num-
duction rate in comparison with the other cases. The ber of operating superposed discharge type ozonizer was
discharge spaces of IESDO and CESDO are much wider three, the maximum ozone yield was obtained at a rate
than that of CISDO, but the ground electrode area of of supplied oxygen gas of 16 `/min because the ozone
IESDO is much larger than that of CESDO. Also, the dis- concentration with IESDO was high.
charge between CE-IE and the discharge between CE-EE When the oxygen gas was supplied at a rate lower than
are superposed in the discharge space in case of IESDO. 4 `/min for three operating ozonizers, the ozone yield was
These result in an activation of the silent discharge and low compared to that for one operating ozonizer. This
improve the ozone concentration and yield. results from ozone concentration, space density augmen-
The ozone yield, given by the product of the discharge tation, and ozone dissociation reactions such as
power by the ozone generation amount, depends on the O + O3 → 2O2 (5)
amount of ozone generated when the discharge power is
fixed. The maximum ozone generation occurred when O3 + e → O2 + O + e (6)
the decrement of the ozone concentration and the incre-
ment in the quantity of ozone generation were equal to Figure 6 shows the ozone yield rate, η, as a function
each other. In this point of view, rate of supplied oxygen of the rate of supplied oxygen gas for the three kinds of
gas at which maximum ozone generation was increased superposed discharge type ozonizers. At this time, ozone
with increasing ozone concentration because decrease ra- yield rate, η was compared with ozone yield of IESDO
tio in the quantity of ozone generation decreased with and CESDO about ozone yield of CISDO. When the
increasing rate of supplied gas [16–18]. number of operating superposed discharge type ozonizers
As shown in Figure 5(a), (b), and (c), when the num- was one or three, η was classified as η1 or η3 , respectively.
ber of operating superposed discharge type ozonizer was The values of the ozone yield rates for the three kins of
one, the maximum ozone yield was obtained when the a superposed discharge type ozonizer occurred in the or-
oxygen gas was supplied at a rate of 4 `/min because the der ESDO > CESDO > CISDO. The silent discharge
Improvement of Ozone Yield by a Multi-Discharge Type Ozonizer· · · – Hyun-Jig Song et al.
Fig. 7. Absorption characteristics of an organic compound
in the visible region for various contact times, τ , of ozone and
dyeing wastewater.
Fig. 8. Photographs of the dyeing wastewater when τ is 1
min and 30 min, respectively. (a) τ = 1 min, (b) τ = 30 min
plasma effects on ozone generation was largest for the
IESDO with a big outer discharge gap space.
Figures 7 and 8 depict the decolorization effect 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, τ , for an ozone concentration of
17185 ppm produced from IESDO in dyeing wastewater.
Figure 8 shows photographs of a dyeing wastewater
when τ is 1 min and 30 min, respectively.
The adsorption decreases as τ is prolonged, and dye-
ing wastewater that is yellowish brown becomes white.
Therefore, a multi-discharge type ozonizer can be used
for water environment improvement.
IV. CONCLUSIONS
A new multi-discharge type ozonizer, utilizing a super-
position of a silent discharge plasma with two discharge
spaces and three electrodes, is proposed to investigate
-1187-
the silent discharge, ozone generation, and the environ-
ment improvement characteristics as functions of the rate
of supplied oxygen gas, as well as the form and the num-
ber 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 difference were applied to two
electrodes and the other electrode was grounded.
The three kinds of superposed discharge type
ozonizers had different discharge and ozone gen-
eration characteristics.
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 gener-
ation 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 oxy-
gen gas. Also, the ozone yield of the multi-
discharge type ozonizer was proportional to the
number of operating superposed discharge type
ozonizers and the rate of supplied oxygen gas.
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.
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