Destruction of Volatile Organic Compounds Used in A Semiconductor Industry by A Capillary Tube Discharge Reactor
Destruction of Volatile Organic Compounds Used in A Semiconductor Industry by A Capillary Tube Discharge Reactor
Destruction of Volatile Organic Compounds Used in A Semiconductor Industry by A Capillary Tube Discharge Reactor
Abstract— Nonthermal plasma technologies offer an innova- [2], [5], [11], dielectric barrier discharge [3], [14], [33], surface
tive approach to the problem of decomposing various volatile discharge [14], [18], [19], [21], [24], ferroelectric packed-bed
organic compounds (VOC’s). We focused on dc capillary tube [2], [5]–[10], electron beam [26]–[32], and flow-stabilized dc
discharge plasma reactors to study the decomposition/destruction
efficiency for toluene, EGM, trichloroethane, and trichlroethylene discharge processes [4], [12], [20], [22], [23]. For a recent
at 50–2300-ppm levels in dry air. The effects of gas flow rate, review, see [36].
VOC concentration, and reactor operating conditions on decom- Plasma chemical processes have been known to be highly
position and analysis of reactant conversion for each VOC were effective in promoting oxidation, enhancing molecular dis-
investigated. The results show that VOC destruction efficiency sociation, and producing free radicals to enhance chemical
as high as 90% can be achieved, even under a short residence
time (3.8 ms) with a destruction energy efficiency of up to 95 reactions. In nonthermal plasmas, electron mean energies are
g (VOC)/kWh. Laboratory-scale plasma technology was success- considerably higher than those of the components of the
fully demonstrated for its potential application for VOC control ambient gas. The majority of the electric energy goes into
in the semiconductor clean-room environment. the production of energetic electrons, rather than into the
Index Terms—Aerosols, capillary tube discharge reactors, envi- heating of gas and ions. The energy in the plasma is, thus,
ronmental technology, gas discharge, nonthermal plasma, plasma directed preferentially to the electron-impact dissociation and
chemistry, volatile organic compounds. ionization of the background gas to produce radicals that, in
turn, decompose the targeted toxic air or VOC’s. This is in
I. INTRODUCTION contrast to the use of thermal plasma furnaces or torches and
several chemical techniques in which the whole gas is heated
(a)
(b)
Fig. 1. (a) Schematics of the experimental setup. (b) Schematics of the capillary tube discharge reactor.
by a packed-bed plasma reactor [5]–[10]. The nonthermal A laboratory-scale capillary tube plasma reactor was in-
plasma approach was deemed to be most appropriate for low- vestigated to control toluene (C H CH ), EGM (C H O ),
concentration VOC applications [4]–[7]. Despite the fact that trichloroethane (C H Cl ), and trichloroethylene (C HCl ) at
some gas heating takes place during the discharge, the basic 50–2300-ppm levels in dry air. This study developed baseline
assumption of nonthermal plasma (different temperatures of engineering data to demonstrate the feasibility of the plasma
charged and neutral species) remains likely valid in all cases reactor for the destruction of various VOC’s at the above ppm
considered in the present paper. levels.
KOHNO et al.: DESTRUCTION OF VOC’S USED IN A SEMICONDUCTOR INDUSTRY 955
(a) (b)
Fig. 2. (a) Typical current and voltage waveforms of capillary tube reactor discharges. (b) Single-pulse current waveform and voltage waveform of
capillary tube reactor discharges.
III. FUNDAMENTAL CHARACTERISTICS OF CAPILLARY Fig. 4. Pressure drop characteristics of capillary tube discharge reactor with
and without gas discharges.
TUBE DISCHARGE REACTORS
A. Current–Voltage Characteristics frequency, and applied dC voltage is effected by a spark, as
Typical current and voltage waveforms are shown in Fig. shown in Fig. 2(a). Fig. 2(b) shows a single pulse current
2(a). In this case, spark discharges are repeated at 4-kHz waveform and corresponding voltage waveforms. The current
956 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 34, NO. 5, SEPTEMBER/OCTOBER 1998
(a) (b)
Fig. 5. (a) Destruction efficiency of toluene as a function of gas flow rate and (b) discharge current for various initial concentrations.
pulse height can be as high as 20 A, and pulsewidth is pressure and/or the effect of the increase of concentration of
around 200 ns. However, the pulse frequency is low enough to molecular species during the discharge.
avoid significant gas heating. Typical time-averaged discharge
current as a function of applied dc voltage for various VOC’s IV. DESTRUCTION OF TOLUENE
at gas flow rate L/min is shown in Fig. 8. The pressure
difference on the capillary tube ranged from negligible to 2500 Toluene destruction efficiency as a function of gas flow
mm of water, as determined by the manometers at both ends rate for various toluene concentrations at the fixed discharge
of the tube. The time-averaged current–voltage characteristics current is shown in Fig. 5. Fig. 5 shows that the destruction
show negative differential conductivity with efficiency of toluene gas nonmonotonically decreases with in-
the polarity, such as the applied voltage (gas flows from the creasing gas flow rate (or decreasing residence time) of VOC’s
negative to positive electrode). Fig. 3 shows that the discharge in a plasma channel. The destruction efficiency of toluene also
current is significantly influenced by a type of trace VOC increases nonmonotonically with increasing discharge current.
in air. However, the current–voltage characteristics are not In a capillary tube reactor, the space occupied by VOC’s
significantly influenced by a gas flow for the case of lower containing air is always under energetic electron showers,
gas flow rate, where the velocity is less than 10 m/s. For a hence, an effective collision between electrons and VOC’s
higher gas flow rate, where the velocity is more than 21 m/s, molecules is proportional to the electrons and/or VOC’s den-
the voltage to obtain a given discharge current increases with sities. The destruction efficiency is approximately proportional
increasing gas flow rate due to the flow stabilized effect, as to the residence time; up to 86% of destruction efficiency
suggested by Chang et al. [1], [12]. is achieved with even 23.4 ms residence time at
mA for a 1246-ppm toluene initial concentration. A slight
increase of the destruction efficiency at higher flow rates (Fig.
B. Pressure Drop Characteristics of Capillary Tube 5) is likely related to nonmonotonic dependency of radical
Discharge Reactors formation and enhancement of discharge stability, due to the
The pressure drop in the capillary tube discharge reactor effective cooling of the electrode. 100% removal of remaining
(Fig. 4) shows an increase with flow rate and the presence toluene and other byproducts is also observed downstream of
of gas discharge. At comparable flow rates (e.g., 9 L/min), the activated carbon filters.
the pressure drop for a 2-mm i.d. is observed to be about five Typical FTIR adsorption spectroscopy output before and
times greater than for an i.d. of 3 mm. The increase of pressure after glow discharge is shown in Fig. 6. Fig. 6(b) shows that
drop with discharge is likely due to the heating effect on gas gaseous byproducts, such as CO , CO, NO , and H O, are
KOHNO et al.: DESTRUCTION OF VOC’S USED IN A SEMICONDUCTOR INDUSTRY 957
(a)
(b)
Q
Fig. 6. (a) FTIR absorption for toluene experiment before discharge at g = 1 L/min and No = 1042 ppm. (b) FTIR absorption for toluene experiment
after discharge at Qg = 1 L/min, V = 11 kV, I = 1 mA, and No = 1042 ppm.
958 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 34, NO. 5, SEPTEMBER/OCTOBER 1998
Fig. 7. Voltage dependence of aerosol particles generation for toluene at Qg = 1 L/min and No = 600 ppm.
produced. Ozone, however, which is commonly generated by dissociation of molecules [14], [15]. For toluene, the reactions
a corona discharge, is not clearly observed, since a capillary of toluene with radicals (such as O and O ) are insignificant,
tube high-energetic plasma may destroy ozone, due to the heat except OH radicals, where the reaction rate of these radicals
generated by gas discharges. In addition to gaseous byproducts, are [16]
a significant amount of brown particles deposited near the exit
side of the plasma reactor is observed. Toluene is dissociated C H CH O
to CO and CO as gaseous compounds, mainly to form C H CH O H: cm /s
carbon and nitrogen hydride bonded particles and tears. Fig. 7 C H CH O
shows the voltage dependence of aerosol particles generated, C H CHO H O: cm /s
where the maximum aerosol particle density coincides with the
C H CH OH
maximum toluene destruction efficiency, as shown in Fig. 5(a).
The principle processes of the VOC’s destruction induced C H CH H O: cm /s
by energetic electrons in plasma are electron and radical impact C H CH OH: cm /s
KOHNO et al.: DESTRUCTION OF VOC’S USED IN A SEMICONDUCTOR INDUSTRY 959
(a) (b)
Fig. 9. Destruction efficiency of trichloroethylene as a function of (a) applied voltage and (b) gas flow rate.
On the other hand, the charge transfer reactions of toluene produced by plasma processes where O , CO, CO , NO , and
with ions and recombination of toluene ions and electrons are H O are also observed as discharge byproducts [14].
significant [16] Hence, the mechanism of toluene destruction by an ener-
getic electron induced plasma process can be summarized as
C H CH O , O , N , or N follows:
C H CH O, O , N, or N : cm /s 1) dissociation and ionization of O , N , and toluene by
C H CH e C H CH : cm /s electrons to form O, O , N, H, hydrocarbon radicals,
and ions;
However, the ion densities are much lower, by 4–5 orders 2) formation of OH radicals from radical atom–molecule
of magnitude, compared with radical densities. Hence, the and ion–molecule reactions [16], [36];
following energetic electron impact dissociations may provide 3) dissociation of toluene by OH radicals and negative ions
additional probable reaction channels (see Fig. 8): to form hydrocarbons;
4) oxidation of hydrocarbons to form CO, CO , and H O;
C H CH C H CH 5) oxidation of nitrogen and oxygen to form NO and O
C H CH H [13], [15] and finally trace N O and HNO formations
C H C H [15];
C H C H 6) formation of aerosol particles by ion induced aerosol
formations [15] from hydrocarbons and nitrates.
since the electron density is as high as 10 cm in the
discharge channel [34], where the reaction rate is of the
order of 10 cm /s and a function of electron mean en- V. DESTRUCTION OF TRICHLOROETHYLENE
ergy [16]. Significant amounts of COOH H, COOH CH , Fig. 9 shows the destruction efficiency of TCE for various
COOH C H , N H CH , and OH C H molecules observed discharge currents and gas flow rates. Dissociation efficiency
in aerosol particles [6], and C H observed in a gas phase [14], at currents exceeding 1 mA shows some decrease, likely due
also support existence of the above electron impact dissociated to falling current–voltage characteristics of gas discharge. The
byproducts formation channels. The dissociated byproducts are flow rate dependence for destruction efficiency of TCE shows
also reacting with oxygen, nitrogen, and hydrogen free radicals greater destruction efficiency for lower flow rates.
960 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 34, NO. 5, SEPTEMBER/OCTOBER 1998
(a)
(b)
Fig. 10. Typical FTIR spectrum (a) before and (b) after discharge for TCE at Qg = 1 L/min.
KOHNO et al.: DESTRUCTION OF VOC’S USED IN A SEMICONDUCTOR INDUSTRY 961
(a) (b)
Fig. 11. (a) Destruction efficiency of trichloroethane as a function of discharge current at Qg = 1 L/min. (b) Destruction efficiency of EGM as a
Q
function of discharge current at g = 1 L/min.
Typical FTIR spectra for TCE before and after capillary tube activated carbon filters which were installed before exhaust,
discharge are shown in Fig. 10. The major discharge byprod- as the other discharge byproducts. The experiments also show
ucts are CO , CO, NO , HCl, and COCl . Their (relative) that the formation of aerosol particles is significantly reduced
concentrations show comparatively weak dependence on the under corona discharge field, since TCE may be destroyed
applied voltage. TCE can be dissociated or ionized by a direct before forming aerosol particles under corona discharges.
electron impact as follows:
C HCl C Cl H VI. DESTRUCTION OB TRICHLOROETHANE
C HCl Cl The TCA destruction efficiency in Fig. 11(a) shows rela-
CHCl CCl tively less variation with current than the TCE test. However,
for TCA, the relative concentrations of discharge products
C HCl
show greater apparent variability than for the TCE case.
C HCl Cl Typical FTIR spectra for TCA destruction tests before and
C Cl H after capillary tube discharge are shown in Fig. 12. The main
products are CO , CO, NO , HCl, NO , and COCl , as shown
since significant high electron concentrations can be generated in Fig. 12. No presence of TCA is detected after the activated
by pulse corona discharges, as described above. carbon filter.
TCE can be destroyed by oxidation processes, due to rad-
icals generated by corona discharges. However, based on the
chemical kinetic model proposed by Chang et al. [14], negative VII. DESTRUCTION OF EGM
ions, such as Cl , C , CO , CO , ClO , HCCl , HC Cl , The EGM destruction efficiency [Fig. 11(b)] peaks at about
etc., may also play an important role in a destruction process. 1.5 mA and is generally higher than the TCA test. Typical
These can be observed from the discharge byproducts, such FTIR spectra for EGM destruction before and after discharge
as H O, CO, COCl , NO , HNO , HCl, and CO . Since HCl are shown in Fig. 13. A somewhat greater variety of products
and COCl are trace as observed in final discharge byproducts, can be deduced from the FTIR spectra. Fig. 13 shows the
Cl , which cannot be observed by FTIR, is considered to presence of CO , CO, N O, NO , and HNO . The latter shows
be a final major chlorine compound. Absorbance peak wave a decrease with the discharge current, while nitrogen oxides
number of 1793 cm is identified as trace COCl species, are either stable or show some increase at higher discharge
however, this peak cannot be found after passing through currents.
962 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 34, NO. 5, SEPTEMBER/OCTOBER 1998
(a)
(b)
Fig. 12. Typical FTIR spectrum (a) before and (b) after discharges for TCA.
KOHNO et al.: DESTRUCTION OF VOC’S USED IN A SEMICONDUCTOR INDUSTRY 963
(a)
(b)
Fig. 13. Typical FTIR spectrum (a) before and (b) after discharges for EGM.
964 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 34, NO. 5, SEPTEMBER/OCTOBER 1998
(a) (b)
(c) (d)
Fig. 14. Energy efficiency of VOC destruction based on plug power EyP and electrical energy used in plasma reactor as a function of discharge power
for (a) toluene, (b) TCE, (c) TCA, and (d) EGM.
Hitoshi Kohno received the D.Sc. degree in bio- Toshiaki Yamamoto (M’97) received the Ph.D. de-
logical and environmental sciences from Saitama gree from the Mechanical Engineering Department,
University, Urawa, Japan, in 1997. Ohio State University, Columbus.
In 1983, he joined Asahikogyosha Company Ltd., He is currently a Professor in the Department
Chiba, Japan, where he is currently a Research of Energy Systems Engineering, Osaka Prefecture
Engineer. He has been engaged in research on University, Osaka, Japan. Prior to this, he was a Se-
air cleaning technologies using nonthermal plasma nior Research Engineer with the Research Triangle
discharge to improve indoor air quality in clean Institute, Research Triangle Park, NC, an Adjunct
rooms or other industrial facilities. Professor and a Research Engineer at the University
Dr. Kohno is a member of the Society of Heating, of Denver, Denver, CO, and a Research Engineer
Air-Conditioning and Sanitary Engineers of Japan, with United McGill Corporation, OH. His research
Japan Association of Aerosol Science and Technology, and the Institute of interest is the application of electrostatics, including nonthermal plasma
Electrical Engineers of Japan. technology, air pollution control, indoor air quality, and electrohydrodynamics
and microcontamination control research. He is the author of numerous
publications.
Dr. Yamamoto is a member of Sigma Xi, the Japan Society of Mechanical
Engineers, Institute of Electrostatics Japan, American Society of Heating,
Alexander A. Berezin received the Ph.D. degree Refrigeration and Air Conditioning Engineers, and Japan Association of
in theoretical solid-state physics in 1970 from Aerosol Science and Technology.
Leningrad State Univesity, Leningrad, U.S.S.R.
Following several academic appointments in
Leningrad, U.S.S.R., he joined the Faculty of
Engineering, McMaster University, Hamilton, Ont.,
Canada, where he became a Full Professor in Akira Shibuya received the B.Eng. degree in
1996. He has contributed to a variety of subjects electrical engineering from Yamagata University,
of fundamental and applied nature, including Yonezawa, Japan, in 1956.
semiconductor devices, thin films, plasma physics, From 1960 to 1986, he was with Ishikawajima-
electrostatics, isotope effects in physics and biology, Harima Heavy Industries Company, Ltd., where he
corrosion physics, and environmental technology. He has also authored works was engaged in the development and management
on social and philosophical aspects of science and, in particular, on the of electrostatic precipitators. From 1986 to 1990, he
limitations of the peer review system in science. was with Koshin Electric Company. He is currently
with Asahikogyosha Company Ltd., Chiba, Japan,
where from 1990 to 1994, he was the Director of
the Research and Development Center.
Mr. Shibuya is a member of the Institute of Electrical Engineers of Japan.
Jen-Shih Chang (M’90–SM’96) received the
B.Eng. and M.Eng. degrees in electrical engineering
from Musashi Institute of Technology, Tokyo,
Japan, and the Ph.D. degree in experimental space
sciences from York University, Toronto, Ont., Shigeo Honda (M’91) received the M.Sc. degree
Canada. in environmental science from Tsukuba University,
From 1973 to 1974, he was a Researcher Tsukuba, Japan, in 1982.
at the Centre de Recherches en Physique de In 1984, he joined Asahikogyosha Company Ltd.,
l’Environment, CNRS, France. From 1975 to 1979, Chiba, Japan, where he is currently a Research
he was a Project Scientist/Assistant Professor with Engineer. He has been engaged in research and
the Department of Physics and Center for Research development on clean-room technologies for actual
in Experimental Space Sciences, York University. From 1979 to 1986, he was designing.
an Assistant/Associate Professor with the Department of Engineering Physics, Mr. Honda is a member of the Society of Heating,
McMaster University. During 1985–1996, he was a Visiting Professor with Air-Conditioning and Sanitary Engineers of Japan.
Musashi Institute of Technology, Tokyo Denki University, Tokyo University,
University of Sevilla, Joseph Fourier University, University of Poitiers, and
Tokyo University of Agriculture and Technology. Since 1987, he has been
a Professor at McMaster University, where he is involved in research on
applied electrostatics, air pollution control, solid and liquid waste destruction,
and plasma technologies.
Prof. Chang is currently Chair of the Electrohydrodynamics Technical
Committee of the IEEE Dielectrics and Electrical Insulation Society.