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Electrical Engineering in Japan, Vol. 170, No.

1, 2010
Translated from Denki Gakkai Ronbunshi, Vol. 128-A, No. 6, June 2008, pp. 401406

Water Treatment with Pulsed Discharges Generated Inside Bubbles

KEISUKE SATO, KOICHI YASUOKA, and SHOZO ISHII


Tokyo Institute of Technology, Japan

SUMMARY instant of generation. Generation processes utilizing ozone


and H2O2, or ozone and ultraviolet radiation, are more
The parallel operation of pulsed discharges generated expensive than conventional economic treatments, such as
inside bubbles is successfully demonstrated by applying a biological degradation processes. The direct method, in
fast rising voltage to a multielectrode system immersed in which OH radicals are generated by electric discharges in
treated water. A 10 ppm solution of acetic acid, which a humid gas, seems to be a candidate for building a cost-ef-
cannot be decomposed by ozone, was used as a persistent fective process. In an oxygen discharge with water vapor,
material and the acetic acid decomposition efficiency was not only is there direct dissociation of H2O molecules by
evaluated by measuring the total organic carbon (TOC) electrons, but the O radicals produced can generate OH
values of the solution. The electric conductivity of the radicals effectively [1].
solution affected decomposition efficiency because the so- Typical examples of the direct OH generation method
lution resistance, which was inversely proportional to the using discharges are pulsed streamer discharges extending
conductivity, limited the magnitude of the discharge current from the tip of an electrode immersed in water [2, 3], pulsed
flowing along the surface of the bubbles generated by the or DC discharges generated in bubbles in water [4, 5], and
feeding of oxygen or argon gas. With a nine-hole electrode corona discharges generated close to the water surface [6,
system, the discharge power deposited in one discharge was 7]. The authors have successfully demonstrated the decom-
lower, and the acetic acid decomposition efficiency was position of acetic acid in water using a direct reaction
higher, than the values obtained with a single-hole electrode
between water and the DC discharges generated in oxygen
system. Lower discharge power seemed to minimize the
bubbles [8]. However, the efficiency of acetic acid decom-
self-quenching of OH radicals, and resulted in the efficient
position was quite low due to the electrolysis of water. The
decomposition of acetic acid. 2009 Wiley Periodicals,
lifetime of the high-voltage electrode was short due to the
Inc. Electr Eng Jpn, 170(1): 17, 2010; Published online in
high loading of discharge power dissipated within a small
Wiley InterScience (www.interscience.wiley.com). DOI
hole a few hundred micrometers in diameter. A fast-pulsed
10.1002/eej.20918
discharge system was tested to eliminate such drawbacks
with the DC electrode system, and was expected to extend
Key words: plasma in water; pulsed plasma; OH the reaction area using a multihole electrode. The primary
radical; water treatment. features of this pulsed electrode system are as follows.

(1) OH radicals can be generated only in treated


1. Introduction water,
(2) a stable discharge is achieved due to the wall
Advanced oxidation processes utilize hydroxyl radi- stabilization effect related to the small hole,
cals (OH radicals), which have a higher oxidation potential (3) the influence of variations in the water surface is
than ozone, and have been studied extensively, due to the limited because the discharge is generated in a bubble,
demand for full decomposition of persistent harmful com- (4) the reaction area is scalable by multiplying the
pounds in water. The lifetime of OH is less than 1 millisec- number of discharges.
ond, and therefore OH radicals should be utilized at the
In the research reported here, an acetic acid solution
Contract grant sponsor: Grant-in-Aid for Scientific Research (KAK- was used as a persistent material, because acetic acid has a
ENHI), No. 18360133. much lower rate of reaction with ozone, but a higher rate of

2009 Wiley Periodicals, Inc.


1
reaction with OH radicals. It can be said that the successful (a)
decomposition of acetic acid provides proof of an effective
method for an advanced oxidation process [7].

2. Experimental

(b)
2.1 Experimental setup

Figure 1 shows a cross-sectional view of a single-hole


discharge reactor consisting of a water vessel, a stainless-
steel high-voltage plate electrode, a grounded wire elec-
trode, a dielectric spacer, a pulsed voltage source, and a gas
feed pipe. The grounded electrode was ring-shaped and
placed 1 mm above the spacer. The spacer, made of 1-mm-
thick ceramic plate with a center hole 0.2 mm in diameter,
separated an acetic acid solution and a gas. Atmospheric
oxygen (99.9%) or argon (99.999%) gas flowed through a
0.1-mm gap between the spacer and the high-voltage elec- Fig. 2. Schematics of (a) nine-hole electrode and
trode, at a flow rate of 50 sccm. A bubble a few millimeters (b) cross-sectional view of reactor.
in diameter was formed above the center hole, and pulsed
discharges were generated in it by applying pulsed voltages
between the high voltage electrode and the ground elec-
trode immersed in the solution. was switched by a fast semiconductor device (Behlke,
The nine-hole reactor is shown in Fig. 2, where (a) is HTS81), which applied pulsed voltages to the reactor. The
a schematic diagram of a multihole electrode and (b) is a maximum specifications of the pulsed voltage source are
cross-sectional view of the discharge reactor. The pulsed
summarized in Table 1.
discharges were generated simultaneously using the one
The reactor voltage and the current waveforms were
voltage source shown in Fig. 3. A typical gas flow rate for
measured with a 1000:1 high voltage probe (Tektronix,
the nine-hole reactor was 450 sccm, controlled by the mass
P6015A) and a current transformer (Pearson Electronics
flow controller (KOFLOC, 3200). Figure 3 shows the pulse
circuit consisting of a high-voltage DC voltage source Inc., CT4100), respectively. The waveforms were digitized
(HAR-30R40), a charging resistor of 270 , an energy with a high-speed oscilloscope (Tektronix, TDS644B).
storage capacitor of 4.2 nF, a current limiting resistor of 330 Acetic acid (CH3COOH) is decomposed to CO2,
, and a discharging resistor of 2.5 k. The stored charge CH3, and H2O through the advanced oxidation processes.
Therefore, the concentration of total organic carbon (TOC)
in the solution decreases with acetic acid decomposition.
The TOC value of acetic acid is 24 gTOC/mol, and the initial
concentration in this experiment was set as 10 ppm (mg/li-

Fig. 3. Equivalent circuit diagram of pulsed voltage


Fig. 1. Experimental setup. source.

2
Table 1. Specifications of H.V. pulse source

ter) in a 10-ml solution. The TOC concentration was meas-


ured by a TOC analyzer (Sievers, 810).

3. Results and Discussions

3.1 Discharge and decomposition


Fig. 5. Typical applied voltage and current waveforms
characteristics with one-hole electrode
of argon discharges.
reactor

Figures 4 and 5 show the typical voltage and current


waveforms in oxygen and argon discharges, respectively.
age electrode and the bubble surface, which was close
These waveforms were obtained by tenfold averaging, with
against the solution, exceeded a critical value, the discharge
a charging voltage of 8 kV, at a frequency of 3 kHz. The
initiated and the current showed a second peak, correspond-
breakdown voltage of the oxygen discharge was about 5 kV,
ing to discharge initiation. When the conductivity of the
or 2.5 times the breakdown voltage of 2 kV in an argon
solution was increased from 30 S/cm with deionized water
discharge. In Fig. 4, the first peak of the current waveforms
to 90 S/cm with tap water, the current magnitude increased
corresponds to the displacement current, which was a func-
in the discharge sustaining period. As a result, the falling
tion of the residual capacitances associated with the spacer
time of the applied voltage rapidly decreased slightly, and
and the solution. When the voltage between the high-volt-
the value of the sustaining current after 30 ns was larger in
the higher-conductivity water.
The argon discharge was more uniform, and the
second peak of the discharge current was almost doubled,
as shown in Fig. 5. Due to the lower discharge resistivity in
argon, the discharge current was twice as large as that of the
oxygen discharge. From the waveforms in Fig. 5, a larger
discharge current flowed in the initial period than in the
sustaining period.
The discharge energy per pulse was calculated by
time-integrating the products of the current and voltage
values, although the dissipated energy within the solution
was included. In the oxygen discharges, the deposited en-
ergy increased from 0.12 mJ with deionized water and 1.16
mJ with tap water. Small changes in the deposited energy
were found in argon discharges, such as 1.26 mJ with
deionized water and 2.09 mJ with tap water.
The UV and visible emission spectra from the oxygen
and argon discharges were measured using a spectrometer
(Ocean Optics Inc., USB4000), as shown in Fig. 6. The tap
water-based solution was placed in the reactor. OH emis-
Fig. 4. Typical applied voltage and current waveforms sion at 309 nm and O emissions at 777.1 and 844.6 nm [8]
of oxygen discharges. were found. Therefore, reactions (1), (2), and (3) in Table

3
Fig. 7. Time variation of TOC concentration in
solutions with two different electric conductivities
for oxygen of argon discharge.

Fig. 6. Emission spectrum from oxygen and argon


discharges from ultraviolet to visible wavelength.
discharge impedance. The TOC reduction was small in 30
S/cm solution, and with oxygen discharges almost no
decomposition was found. Using a higher solution conduc-
2 are the primary reactions of OH generation in the plasma tivity of 90 S/cm, the TOC reduction increased signifi-
reactor. cantly, particularly with oxygen discharge.
Reactions (4), (5), and (6) represent quenching reac- The reaction rate constant of acetic acid with ozone
tions of OH radicals. As the OH density increases, the is 3 105 mol1s1 [10], and therefore the ozone molecules
quenching reactions limit the decomposition efficiency. generated in the oxygen discharge had little influence on
Figure 7 shows the time variation of the TOC reduc- TOC reduction. In fact, the oxygen or ozonated oxygen gas
tion with one discharge electrode system. The discharge gas feed to the solution showed no TOC reduction as long as
and solution conductivity were changed, as shown in Fig. there was no discharge. The high rate constant with the OH
7. The related voltage and current waveforms are shown in radical, 1.6 107 mol1s1, and the OH emissions from the
Figs. 4 and 5. The voltage applied to the reactor was kept discharges indicate that OH radicals caused the TOC reduc-
constant at 8 kV with a frequency of 3 kHz. Therefore, the tion. The argon discharge showed a slight dependence on
discharge current and also the discharge power deposited the solution conductivity because of the higher stability of
in the discharge column changed along with changes in the the discharges, and a low dependence of the discharge
gas and solution conductivity. The equivalent impedance of energy on the solution conductivity. The peak values of the
the reactor was a function of the water conductivity and the discharge current were 7 A for argon discharges and 2 A for
oxygen discharges. A large amount of OH radicals could be
generated in an argon discharge with reaction (1). However,
the quenching processes expressed by reactions (4) to (6)
Table 2. Primary chemical reactions related to OH could be accelerated in an argon discharge. In oxygen
radicals discharges, the initial peak current was half that of the argon
discharge, and a nearly constant current of 1 A flowed for
200 ns in a 90 S/cm solution, as shown in Fig. 4. This
condition seems to effectively prevent OH quenching.

3.2 Discharge and decomposition


characteristics with nine-hole electrode
reactor
3 1
The units for the reaction rate k are cm s for two-body reaction or Figure 8 shows the typical applied voltage and cur-
6 1
cm s for a three-body reaction. rent waveforms, tenfold averaged, obtained with the nine-

4
Fig. 8. Typical applied voltage and current waveforms
of nine parallel discharges with oxygen gas.

hole electrode reactor. The experimental conditions were: Fig. 10. Input power as a function of charging voltage
charging voltage 8 kV, frequency 1 kHz, oxygen feed, and and frequency in single or nine-hole electrode reactor.
solution conductivity 90 S/cm. Compared with Fig. 4, the
current peak is doubled, and the decay time of the voltage
is decreased. The dissipated energy per pulse is 2.2 mJ. The
visible photograph, taken at an exposure time of 300 ns, varied to change the input power to the reactor. The input
shows that nine parallel operations of pulsed discharges power to the reactor increased with the voltage, but the input
were achieved with this electrode system, as shown in Fig. power with the nine-hole electrode was less than nine times
the value of the input power with the single-hole electrode.
9. The averaged discharge power was a few watts, but the
The power dissipation per hole decreased with the nine-
peak discharge power reached 12 kW. Therefore, discharge
hole electrode. The decomposition rate as a function of the
generation in each hole may be possible by using only one
discharge input power is shown in Fig. 11. The decompo-
pulsed voltage source. However, DC operation required at
sition rate was calculated by the equation
least 40 W of discharge power to sustain one discharge, so
that the limited power of the voltage source failed to gen- (7)
erate multiple discharges with one voltage source.
The dissipated power in the single- or nine-hole
electrode reactor is shown in Fig. 10, as a function of the where t (gTOC/min) is the amount of acetic acid decom-
charging voltage and repetition frequency. In this figure, posed per minute, C (ppm) is the reduction in TOC, w (g)
both the charging voltage and the repetition frequency were

Fig. 9. Still photograph of nine parallel oxygen


discharges driven by 8-kV, 1-kHz voltages. Fig. 11 Decomposition rate as a function of input
Exposure time was 300 ns. power.

5
is the weight of the solution, and t (min) is the processing 4. Conclusions
time. The decomposition rate increased with the discharge
input power. This is because the number of OH radicals By parallel operation of pulsed discharges inside
increased with the current magnitude, which was a linear bubbles in treated water, we successfully demonstrated the
function of the input power, through reactions (1) to (3). decomposition of acetic acid, used as a persistent substance.
Higher repetition frequencies resulted in large amounts of The higher solution conductivity increased the magnitude
OH radicals. of the discharge current, and resulted in a higher decompo-
The decomposition energy efficiency e (gTOC/kWh) sition rate of acetic acid. Parallel operation using a single
was calculated as follows, where f (Hz) is the repetition driving circuit was achieved by using fast rising pulsed
frequency, V (V) is the charging voltage, and I (A) is the voltages. The maximum decomposition rate and efficiency
discharge current: were 19.8 g/min and 0.35 g/kWh, respectively. Effective
utilization of OH radicals can be achieved by lowering the
(8) discharge input power by preventing the mechanisms of
quenching of OH radicals. Parallel operation of pulsed
Unlike the decomposition rate, the decomposition energy discharges seems to be suited to realizing an efficient reac-
efficiency rapidly decreased with increasing input power, tion field for utilizing OH radicals.
as shown in Fig. 12 for the single-hole and the nine-hole
electrode reactors. This result shows the crucial effects of Acknowledgment
quenching of OH radicals on the decomposition efficiency.
Increasing the frequency had little influence on energy This work was supported by a Grant-in-Aid for Sci-
efficiency, and seemed not to enhance the OH reduction entific Research (KAKENHI), No. 18360133.
shown by Eqs. (4) to (6). As indicated by Fig. 12, the
decomposition efficiency with a single hole in 5-kHz op-
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AUTHORS (from left to right)

Keisuke Sato received his B.E. and M.E. degrees from Tokyo Institute of Technology in 2006 and 2008 and went to work
for GE Yokogawa Medical Systems, Ltd.

Koichi Yasuoka (member) received his B.E., M.E., and D.Eng. degrees from Tokyo Institute of Technology in 1978, 1980,
and 1983. From 1983 to 1995, he was engaged in the development of high-power lasers at Toshiba Corporation. In 1995, he
joined the Faculty of Engineering, Tokyo Institute of Technology, and is currently a professor in the Department of Electrical
and Electronic Engineering. His research interests include plasmawater interactions, the electrohydrodynamic effect, and their
applications.

Shozo Ishii (member) received his B.E., M.E., and Ph.D. degrees in electrical engineering from Tokyo Institute of
Technology in 1968, 1970, and 1973 and joined the Faculty of Engineering. From 1973 to 1975, he was affiliated with the
Department of Physics, University of British Columbia, Canada. He is currently a professor in the Department of Electrical and
Electronic Engineering, Tokyo Institute of Technology. His research interests are atmospheric microplasmas and their
applications.