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Atmospheric plasma-driven catalysis for the low temperature decomposition of dilute aromatic

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2005 J. Phys. D: Appl. Phys. 38 1292

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INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 38 (2005) 1292–1300 doi:10.1088/0022-3727/38/8/029

Atmospheric plasma-driven catalysis for

the low temperature decomposition of
dilute aromatic compounds
Hyun-Ha Kim1 , Atsushi Ogata and Shigeru Futamura
National Institute of Advanced Industrial Science and Technology, AIST Tsukuba West,
16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan
E-mail: hyun-ha.kim@aist.go.jp

Received 30 November 2004, in final form 8 February 2005

Published 1 April 2005
Online at stacks.iop.org/JPhysD/38/1292

Abstract
The decomposition of volatile organic compounds (VOCs)—six aromatic
compounds of benzene derivatives and formic acid—was investigated using
a plasma-driven catalysis (PDC) system at atmospheric pressure. In the
PDC reactor, the decomposition efficiency of VOCs was mostly determined
by the specific input energy (SIE) and insensitivity to the gas hourly space
velocity from 11 000 to 55 000 h−1 . Formic acid (HCOOH) was formed as a
common intermediate from the decomposition of the tested aromatic
compounds. Formic acid was also found to be an important intermediate for
CO2 formation. Except for styrene, all the tested VOCs indicated zero-order
kinetics, which confirm the dominant role of the catalytic reaction in the
decomposition of VOCs using the PDC reactor. A simple kinetic model
represents well the observed zero-order kinetics with respect to the SIE.
Unlike conventional plasma reactors, no correlation between the ionization
potential and the decomposition was found with the PDC reactor.
Continuous operation tests indicated stable performance without
deterioration of catalytic activity over 150 h.
(Some figures in this article are in colour only in the electronic version)

1. Introduction
Air pollution problems related to the emission of volatile
organic compounds (VOCs) have been the subject of
considerable research interest, because VOCs cause the
secondary problem of photochemical smog in the troposphere,
as well as being toxic on their own. Many of these VOCs are
hazardous to health and the environment, so their emission
is strictly regulated in many countries. There is a wide
range of available end-of-pipe technologies for the abatement
of VOCs, each having advantages and drawbacks. The
main advantages of nonthermal plasma (NTP) technology
include moderate operating conditions (atmospheric pressure
and room temperature), rapid start-up, compact system, and so
on. There have been extensive studies on NTP application to
pollution control over the last two decades [1–3]. Substantial
1 Author to whom any correspondence should be addressed.
progress has been made during this period. Recently, the
practical use of NTP technology in the field of air pollution
control begun in many countries [4]. NTP technology is now
faced with an important turning point of further development
and extended use in industries. Two hot issues are the
reduction of energy consumption and the suppression of
reaction by-products.
One of the major current trends in NTP research is
the combination of NTP with catalysts [5–11]. In the
NTP application of VOC decomposition, the improvement of
reaction selectivity is highly important in terms of reaction
by-products. This NTP–catalyst hybrid system can enhance
the removal efficiency and the reaction selectivity [12].
The authors have investigated the decomposition of benzene
using a single-stage plasma–catalyst hybrid system, which
is also referred to as a plasma-driven catalysis (PDC)
[13, 14]. The PDC system takes advantage of a synergy
between NTP chemistry and catalytic reaction for relatively

0022-3727/05/081292+09$30.00 © 2005 IOP Publishing Ltd Printed in the UK 1292


low temperature conditions. It has been reported by the
authors that the PDC reactor packed with Ag/TiO2 catalyst is
superior to the conventional gas-phase NTPs in terms of energy
efficiency, carbon balance and selectivity of carbon dioxide
[15]. Measurements of nanometre-sized aerosol formation
in the PDC reactor provided supporting evidence for the
good carbon balance, usually at around 100%. On the other
hand, the conventional NTP reactors produced a significant
amount of nanometre-sized aerosols. The other discriminative
characteristics of the PDC reactor over the conventional
gas-phase homogeneous plasma reactors are in the kinetics.
Basically, the chemical reactions in NTP reactors are energy-
dependent processes rather than being dependent on the gas
residence time. This is also rationalized by the fact that the
characteristic time of the plasma chemical reactions is usually
short enough relative to the gas residence time. Therefore,
the kinetics for the gas removal using plasma reactors has
been expressed as a function of energy (dC/dE) in contrast to
the conventional method, which express the gas removal as a
function of time (dC/dt). Many published studies indicate that
the dominant kinetics of the gas-phase plasma reaction is first-
order in the concentration [16–20]. Similar first-order kinetics
was also reported in an early study on the NOx removal [21] and
recent studies for the decomposition of VOCs [22–25] using
an electron-beam generated gas-phase plasma. On the other
hand, the zero-order kinetics observed in the decomposition
of benzene with the PDC reactor clearly demonstrates that
the catalytic surface reaction plays the dominant role in the
decomposition process [26].
Since the decomposition of VOCs is often strongly
affected by their chemical structures [27], it is necessary
to know the structure-dependent characteristics for a given
plasma reactor. The main objective of this work is
to investigate the capability of the PDC reactor for the
decomposition of various aromatic VOCs at relatively low
concentrations. In a previous publication [26], we reported that
the maximum applicable energy to the plasma reactor should be
determined not only by the decomposition efficiency of VOCs
but also by the formation of nitrogen oxides. In this sense,
the concentration range of the tested VOCs was set at around
100 ppmv except for space velocity-related tests. Six aromatic
compounds of benzene derivatives (benzene (C6 H6 ), toluene
(C6 H5 CH3 ), styrene (C6 H5 CHCH2 ), o-, m- and p-xylene
(C6 H4 (CH3 )2 ) and formic acid (HCOOH)) were tested in this
study. Toluene and xylene rank form the major part of the total
VOC emission in Japan. The decomposition of formic acid
was investigated to elucidate the decomposition pathway of
the aromatic compounds, because formic acid was a common
ring cleavage intermediate in the decomposition of aromatic
compounds. The important factors that must be considered in
the decomposition of VOCs using NTP technology, are the
carbon balance and the selectivity of CO2 . The influence
of space velocity on the performance of the PDC reactor
was also investigated. It has known from the literature that
the ionization potential (IP) has some correlation with the
decomposition efficiency of VOCs using NTP reactors. This
correlation was also examined for the PDC system. Results of
a continuous operation test over 150 h will also be presented.
Decomposition of dilute aromatic compounds
2. Experimental
2.1. Experimental set-up and the PDC reactor
Figure 1 shows the experimental set-up used in this study.
The experimental set-up consisted of gas cylinders, a water
bath, a PDC reactor, an ac power supply, an oscilloscope
for voltage–current measurement and gas measurement
instruments. The details of the PDC reactor and the catalyst
preparation are described in detail in previous work [13, 14],
and only a brief description is given here. The inner diameter
and the effective length of the glass tube were 13 mm and
200 mm, respectively. A coil-type electrode made of stainless
steel (0.45 mm diameter) was set inside the tube as a high-
voltage electrode, and silver-paste was painted on the outer
surface of the reactor tube (quartz) as a ground electrode.
This modification of the electrode configuration reduces the
abnormal discharge on the outer surface of the reactor, resulting
in higher energy efficiency [14]. The PDC reactor was placed
in an oven with the temperature maintained at 100˚C. The
catalyst packed in the PDC reactor was a Ag supported TiO2
catalyst. The BET (Brunauer–Emmet–Teller) surface area of
the TiO2 (Sakai Chemicals Co.) catalyst was 68 m2 g−1 . The
mean diameter of the Ag/TiO2 catalyst was about 1.8 mm.
The amount of Ag catalyst loaded on the TiO2 catalysts was
2.0 wt%. The silver catalyst was loaded on the TiO2 pellet by
an impregnation method using AgNO3 (Wako Ltd.: Research
grade) standard solutions. The surface of the Ag/TiO2 catalyst
before and after the reactions was analysed using field emission
type scanning electron microscopy (FE-SEM, TOPCON Co.,
DS-720).
2.2. Gas measurement
Concentrations of the tested VOCs were adjusted by changing
the bubbling flow rate or the temperature of the water bath.
Some modifications were made in gas analysis in view of
the experimental requirement in this work. Two on-line
Fourier transform infrared (FTIR) spectrometers (Perkin
Elmer, Spectrum One) were used for simultaneous and
quantitative gas analysis of VOCs, CO, CO2 , NO, N2 O,
NO2 and formic acid (HCOOH). One is for measuring the
concentration of VOCs at the inlet of the plasma reactor.
The other is for measuring the outlet VOC concentration
and the reaction products. Based on these simultaneous
measurements of reactants and the reaction products, the
material balance and the product selectivity were determined
with higher accuracy. One important advantage of FTIR
gas analysis over the well-established gas chromatography
method (GC) is that it does not interfere with ozone. In
the case of GC analysis, coexisting ozone in the sample gas
may cause additional decomposition of VOCs in a column,
resulting in the overestimation of decomposition efficiency.
Another advantage of FTIR measurement is the relatively good
sensitivity towards HCOOH. The flame ionization detector
(FID), the most widely used GC detector for the measurement
of VOCs, has poor sensitivity to HCOOH [28]. The two
FTIR spectrometers are equipped with a gas cell of 6.4 m
optical pathlength and a TGS detector. A time-base software
(Perkin Elmer) was used for the continuous measurement of
gas concentration at 2 min intervals by averaging five scans
1293
H-H Kim et al
Figure 1. Experimental set-up.
CH3
CH
O frequency were set with the function generator. The input
H C O H
Formic acid Benzene Toluene Styrene
CH 3
CH3 CH3
CH3
CH3 CH3
o-xylene m-xylene p-xylene
Figure 2. Chemical structures of the tested VOCs.
with a resolution of 1 cm−1 . All the data shown in this
work were recorded after the stationary state was reached
for given conditions. One test run at fixed condition took
about 10 h with increasing specific input energy (SIE). Both
the gas cells (0.75 L) were heated to 343 K to prevent any
possible condensation during the measurement. Detection
limits of the FTIR measurement vary with the resolution and
the optical pathlength. With the measurement conditions of
the FTIR the detection limits for the gas components were
2.1–8 ppmv. The gas flow rate was regulated using mass flow
controllers (KOFLCO, CR-300). A typical gas composition
was VOCs (75–110 ppmv)–O2 (20%)–N2 (balance). The
total gas flow rate was 4 litre per min (LPM) at standard
conditions (293 K, 0.1 MPa) unless otherwise noted. The gas
hourly space velocity (GHSV) was about 22 000 h−1 at 4 LPM.
The chemical structures of the VOCs tested in this work are
described in figure 2. It should be noted that styrene has
a carbon double bond that is very reactive to the ozone attack.
The details of this will be discussed later.
2.3. Electrical measurement
The PDC reactor was energized with an ac high-voltage power
supply. The ac high-voltage power supply consisted of a
high voltage amplifier (Trek, 20/20B) and a function generator
1294
(Tektronix, AFG 310). The input parameters of voltage and
CH2
signal from the function generator was amplified 2000-fold
by the Trek 20/20B and then applied to the PDC reactor.
The V –Q Lissajous figure method was used to determine the
discharge power in the PDC reactor. For the measurement
of charge (Q) a capacitor of 100 nF connected in series
to the ground line of the plasma reactors was used. The
voltage across the capacitor, which was proportional to the
charge Q (i.e. time-integrated current), was measured with a
10 : 1 voltage probe (Tektronix, P6109B). The high voltage
(V ) applied to the PDC reactor was measured with a 1000 : 1
high voltage probe (Tektronix, P6015A). The waveforms of
the applied voltage and the charge were recorded with a
digitizing oscilloscope (Tektronix, TDS3032) by averaging
64 scans. The area of the V –Q parallelogram indicates the
energy dissipated in the PDC reactor during a single cycle of
ac high voltage. The discharge power was then calculated
by multiplying the area of the V –Q plot with the frequency.
When a voltage of 28 kVpk–pk was applied to the PDC reactor
the average discharge power was around 25 mJ cycle−1 . The
SIE was calculated using the following relation.
discharge power (watt)
SIE (J L−1 ) = × 60. (1)
gas flow rate (L min−1 )
The SIE value was varied by changing either the applied
voltage or frequency from 100 Hz to 1.5 kHz.
3. Results and discussion
3.1. The influence of GHSV
GHSV is one of the key factors in determining the performance
of conventional thermal catalyst processes. Changes in
GHSV drastically affect the performance of conventional
thermal catalysis [29]. As mentioned above, gas-phase NTP
processes are usually not influenced by the GHSV (i.e. gas
residence time) because the gas-phase chemical reactions
involving radicals (such as N, O(1 D), O(3 P), OH, HO2 , etc)
terminate in a very short time (usually within 0.1 ms). It is,
therefore, important to know the influence of space velocity

Benzene concentration (ppm)
200
150
100
50
0
0 100 200
-1
Specific input energy (J L )
Figure 3. The influence of GHSV on the performance of the PDC
reactor. The solid line is the fit to the experimental data points.
and the optimum range on the abatement of VOCs using the
PDC system. Figure 3 shows the experimental results of
benzene decomposition by varying the GHSV from 11 000 to
55 000 h−1 . In contrast to conventional thermal catalysis the
change of GHSV did not affect benzene conversion as long as
the SIE was kept constant. The experimental data points fell
on a single line regardless of the GHSV conditions. In other
words, the SIE is the key scaling factor of the PDC system, as
in the case of the gas-phase plasma chemical reactions. From
a practical point of view, this GHSV-independent reaction
behaviour is promising because the PDC system can be
successfully used for the removal of the VOCs without any
trouble even under a significant change in flow rate.
3.2. Chemical structure-dependent behaviour of the aromatic
compounds
Figure 4 shows the semi-log decay of VOC concentration as
a function of SIE. This kind of plot also provides additional
important information on the kinetics. Except for styrene, the
other five aromatic compounds tested showed very similar
trends regardless of their chemical structure. There was
also no marked difference in the removal efficiency for o-,
m- and p-xylene. The different behaviour of the styrene
decomposition can be explained by its higher reactivity towards
ozone.
Styrene + O3 → product (k = 3.0 × 10−17 cm3 mol−1 s−1 ).
(R1)
The reaction rate constant for the styrene–O3 reaction is
larger by around 3–5 orders of magnitude than those for
the other five aromatics at 300 K [30]. However, this high
conversion of styrene even at low SIE values does not mean
a higher decomposition performance, because of the poor
carbon balance (see below). These results indicate that
intermediates from the ozone–styrene reaction were deposited
on the surface of the catalyst. Formic acid, which was the
common intermediate from the aromatic compounds, was
decomposed more easily than the aromatic compounds.
Since the formation of nitrogen oxides increase with
the SIE, the optimum operating condition of SIE should be
determined based on both VOC decomposition efficiency and
Decomposition of dilute aromatic compounds
Formic acid - 76 ppm
110 00 h-1 Benzene - 110 ppm
220 00 h-1 Styrene - 100 ppm
330 00 h-1 Toluene - 101 ppm
440 00 h-1 o -xylene - 100 ppm
550 00 h-1 1.0 m -xylene - 75 ppm
p -xylene - 100 ppm
[C]/[C]0
0.1
300
0 50 100 150 200
–1
Specific input energy (J L )
Figure 4. Semi-log plot of concentration of VOCs versus SIE.
by-product formation. All the tested VOCs were completely
decomposed with a SIE of about 130 J L−1 , where the
concentrations of N2 O and NO2 formed were 11 ppm and
38 ppm, respectively.
3.3. Decomposition products, carbon balance and CO2 yield
In the cases of aromatic compounds tested in this study, the
formation of CO and CO2 account for most of the carbon
from VOC decomposition. Formic acid was the common
intermediate from the decomposition of aromatic compounds,
but its yield was lower than those of CO and CO2 . No other
ring-cleavage or ring-retaining products were detected from
the gas analysis using FTIR. Figure 5 shows the concentration
of HCOOH from the decomposition of aromatic compounds.
The formation behaviour of HCOOH can be classified into
two patterns. In the cases of styrene, toluene and p-xylene,
the formation of HCOOH was largest below 40 J L−1 and
decreased with increasing SIE. On the other hand, HCOOH
concentrations went through a maximum at a certain SIE and
then decreased with further increase in the SIE. Unlike other
aromatic compounds o-xylene produced no HCOOH.
Figure 6 shows the carbon balance data as a function
of SIE. Carbon balance was simply calculated from the sum
of CO, CO2 and HCOOH, which were the only measurable
gaseous products in this study.
[CO] + [CO2 ] + [HCOOH]
Carbon balance (%) = × 100.
n([VOC]0 − [VOC])
(2)
Here, [VOC]0 and n indicate inlet concentrations of VOC and
the number of carbon atoms in them, respectively. Carbon
balance data for formic acid, benzene and toluene were good at
around 100%. In the cases of o-, m- and p-xylene; however, the
carbon balance slightly exceeded 100% at >120 J L−1 . These
observations indicate that the deposition of some intermediates
from the decomposition of o-, m- and p-xylene occurred at low
SIE. Good carbon balances in the PDC reactor also indicate
1295
H-H Kim et al
50
HCOOH concentration (ppm)
40
30
20
10
0 0
0 50 100
Specific input energy (J L–1)
Figure 5. Formic acid formation resulting from the decomposition
of aromatic compounds. The concentrations of VOCs are the same
as in figure 4.
Carbon balance (%)
100
50
0 decomposition of adsorbed VOCs using oxygen plasmas [31].
0 50 100
Specific input energy (J L )
Figure 6. Carbon balance plots for the decomposition of VOCs
using the PDC reactor. The symbols are the same as in figure 4.
that the formation of other reaction by-products, such as
aerosols and smaller organic compounds was negligible. In our
previous work, we reported that a large amount of nanometre-
sized aerosol was produced from the decomposition of benzene
with gas-phase plasma reactors, where the carbon balance was
also poor at 63–90% [19]. The good carbon balance with the
PDC reactor also showed that the contribution of adsorption to
the benzene removal could be ignored.
It is desirable to achieve deep oxidation to CO2 rather
than CO in the oxidative decomposition of VOCs. In this
sense, the CO2 yield can be a useful parameter to assess the
performance of a PDC system towards VOC decomposition.
Figure 7 shows a comparison of CO2 selectivities obtained
for different compounds. The CO2 selectivity (SCO2 ) was
calculated as follows:
[CO2 ]
SCO2 (%) =
[CO2 ] + [CO]
The selectivities of CO2 in COx were not dependent on
either the SIE or the type of VOCs, and showed constant
values. This observation indicates that the channel to produce
CO2 was determined by the decomposition pathway (i.e. the
1296
100
Toluene
Styrene
CO2 selectivity (%)
Benzene 75
o-Xylene
m-Xylene
p-Xylene
50
25
0
50 100 150 200
150 200
–1
Specific input energy (J L )
Figure 7. Selectivity of carbon dioxide. The symbols are the same
as in figure 4.
type of intermediates). Again, once CO is formed, further
oxidation of CO to CO2 in the PDC reactor is negligible under
the tested SIE range. Since the decomposition of HCOOH
preferably produced CO2 in the PDC reactor, HCOOH is
believed to be an important precursor for CO2 formation.
Except for HCOOH which shows 100% CO2 selectivity, five
aromatic compounds showed almost the same CO2 selectivity
at about 71–77%. These similar by-product distributions and
selectivities indicate that the decomposition mechanism of
aromatic compounds in the PDC reactor are quite similar.
Although it is not within the scope of the current study, we
would like to note that further enhancement of CO2 selectivity
is possible by using cycled operations of adsorption and
150 200 250
–1
3.4. Kinetics for the decomposition of VOCs in the PDC
system
The determination of reaction kinetics of chemical reactions in
question is useful in understanding the general characteristics
of the chemicals for a given reactor. It has been reported
in the literature by many authors that the semi-log plots of
concentration as a function of SIE have a linear correlation in
the NTP processing of gaseous pollutants [32–34]. However,
as one can see from figure 4, all the slopes of the tested VOCs
were not linear except for styrene, and became steeper as the
SIE increased. These trends are the typical cases of zero-
order kinetics, where the heterogeneous reaction (catalytic
reaction in this case) plays a dominant role. Our previous data
on benzene decomposition indicate that the roles of thermal
catalytic reaction and UV light from the plasma were negligible
in the PDC reactor packed with Ag/TiO2 catalysts [26]. As a
result, it can be concluded that the decomposition of VOCs
proceeds via the catalyst surface activated by the plasma.
—k1 → CAT∗ .
CAT ←k (R2)
2—
× 100. (3)
Here, CAT∗ indicates activated sites formed on the catalyst
surface by plasma application. The formation of CAT∗ will
be proportional to the discharge power density (Pd ), which is
defined as the discharge power divided by the volume of the
PDC reactor. If there are no adsorbed VOCs on the catalyst
 Decomposition of dilute aromatic compounds
∗
surface, the formed CAT will be deactivated to non-reactive 150

Decomposed amount of VOCs(ppm)

‘CAT’. The CAT∗ formed will further react with adsorbed VOC
(hereinafter VOCAds ) to yield the intermediate and product.
120
k3
−→ Intermediate + CAT (R3)
VOCAds + CAT∗ —|| k4
−→ Product + CAT (R4) 90
k5
Intermediate + CAT∗ −→ Product. (R5)
60
From the FTIR analysis of reaction products, the intermediate
and the product will be HCOOH and COx (CO2 + CO),
30
respectively. As was indicated in figures 5 and 6 the dominant
channel for the VOCAds –CAT∗ reaction will be R4. The
branching ratios of R4, R3/(R3 + R4), simply calculated from 0
the ratio of HCOOH and COx , were higher than 97% for the 0 50 100 150 200
tested VOCs. The reaction rate for the formation of CAT∗ and Specific input energy (J L ) –1
the decomposition of VOCAds can be written as follows:
Figure 8. Decomposed amount of VOCs versus SIE in the PDC
d[CAT∗ ]
= k1 Pd − k2 [CAT∗ ] − (k3 + k4 )[VOCAds ][CAT∗ ] reactor. The symbols are the same as in figure 4.
dt
−k5 [Intermediate][CAT∗ ], (4) Table 1. Energy constants for the tested VOCs.
d[VOCAds ] Energy constant kE
= −(k3 + k4 )[VOCAds ][CAT∗ ]. (5) VOCs (ppm J−1 · L)
dt
Similar to the gas-phase chemical reactions involving free Formic acid 1.25
radicals, the chemical reactions related to CAT∗ are also Benzene 1.01
Toluene 0.79
expected to proceed virtually as rapidly as they are formed. Styrene 0.81
So, we can assume a steady state, where the formation/loss of o-xylene 0.72
[CAT∗ ] is balanced (d[CAT∗ ]/dt ≈ 0). m-xylene 0.68
p-xylene 0.71
k1 Pd
[CAT∗ ] = . (6)
k2 + (k3 + k4 )[VOCAds ] + k5 [Intermediate]
The resulting equation (10) also has zero-order kinetics, which
By substituting equation (6) in equation (5) we can obtain the confirms the experimental results observed in figure 4. A larger
following formula: kE indicates higher capability in the decomposition of VOCs.
Figure 8 presents the amount of VOCs decomposed versus
k1 (k3 + k4 )[VOCAds ]Pd
d[VOCAds ] = − dt SIE. It should be noted that the decomposed amount of styrene
k2 + (k3 + k4 )[VOCAds ] + k5 [Intermediate] is not based on the outlet concentration but is the equivalent
= −kPd dt, (7) amount estimated from the sum of decomposition products.
where In the low SIE range, where the conversion of VOCs is also
low, the decomposed amount of VOCs increases linearly with
k1 (k3 + k4 )[VOCAds ] SIE. In the high SIE range, the decomposed amounts deviate
k= . (8)
k2 + (k3 + k4 )[VOCAds ] + k5 [Intermediate] slightly from the linear line. A plausible explanation for
this slight deviation is that the eliminated terms ‘k2 ’ and
For the typical experimental conditions in this study, loss of ‘k5 [Intermediate]’ in equation (8) become important as the
CAT∗ by natural deactivation can be neglected. Similarly, SIE increases. Increased conversion of VOCs in the high
from the high branching ratio of R4, the reaction R5 is also SIE range may also increase the [intermediate] resulting in the
expected to be less important. Therefore, the terms k2 and decrease of kE . Similarly, deactivation loss of CAT∗ will also
k5 [Intermediate] can be eliminated from equation (8). Since be important as the decomposition efficiency approaches 100%
the integration of the discharge power density (Pd ) over the gas (i.e. low VOCAds on the surface). A similar trend was reported
residence time in the PDC reactor gives the discharge energy for the decomposition of 200 ppmv benzene [26]. Table 1
dissipated per unit gas volume (i.e. SIE; J L−1 ), equation (7) summarizes the energy constants for the six VOCs obtained
can be integrated to yield in this study. As expected from the decay curve in figure 4
HCOOH showed the largest kE of 1.25 ppm J−1 L.
[VOCAds ]0 − [VOCAds ] = −k · SIE. (9) Among the xylenes, m-xylene showed a slightly smaller
kE than those of o- and p-xylene. These kE data for various
The rate coefficient k1 is related to the plasma energy so we VOCs can also be helpful in estimating the energy consumption
can substitute the rate constant of equation (9) by kE , which to achieve the required degree of decomposition.
is defined as the energy constant. Then, we can get a simple
kinetics expression for the decomposition of VOCs in the PDC 3.5. IP versus decomposition efficiency
system:
As was first shown by Nunez et al [35] the IP showed the
[VOCAds ]0 − [VOCAds ] =
[VOC] = −kE · SIE. (10) highest inverse correlation with the destruction efficiency of

1297
H-H Kim et al
Rate constant (cm3 mol-1 s-1)
10-10
10-11
kOH
10-12
10-13
k O(3P)
10-14
8 9 10 11
Ionization potential (eV)
Figure 9. The relationship between the IP of VOCs and the rate
constants for OH radical (kOH ) and atomic oxygen (kO ). The
symbols are the same as in figure 4. Rate constant data were taken
from the NIST database (http://kinetics.nist.gov/index.php).
VOC in a BaTiO3 packed-bed plasma reactor, among the
evaluated parameters, including heat of combustion, size of
the molecule, molecule bonding energy, Gibbs free energy
and enthalpy. The higher the IP the lower the decomposition
efficiency at constant operation conditions. Subsequent studies
confirm this inverse correlation for the decomposition of
aromatic compounds using a BaTiO3 packed-bed plasma
reactor [36, 37]. A similar inverse relationship of the
decomposition of aromatic compounds (benzene, toluene,
ethylbenzene and o-xylene) with the IP was also reported in
a capillary discharge plasma reactor [38]. There has been
no theoretical explanation for the experimental observation
that the IP is correlated with the decomposition efficiency of
VOCs. It is now well established that radical species play
an important role in the gas-phase plasma chemical reactions.
Most of the radicals are electrophilic in nature, and tend to
attack the chemical structure having large electron density.
The IP is the energy required to remove an electron from its
parent molecule or atom. It is, therefore, expected that there
is some relationship between the IP of a certain VOC and its
reactivity to radical species. Figure 9 shows the relationship
between the IP of VOCs and the rate constants for O(3 P) and
the OH radical. VOCs with lower IP usually have a higher
possibility of radical attack. For aromatic compounds tested
in this study kOH is larger than kO(3 P) by approximately two
orders of magnitude. This inverse relationship between the IP
and the rate constants for O(3 P) and the OH radical, although it
is not shown here, is also applicable to other structures, such as
alkanes and paraffins. Therefore, inverse correlation between
the IP and the decomposition efficiency for a group of certain
chemical structure indicates that the radical process plays an
important role in the decomposition and vice versa. According
to the recent results by Hirota et al [24] on the electron-
beam decomposition of various VOCs, a linear relationship
between kOH and the G-value were obtained depending on their
chemical structures. The correlation between the IP and the
rate constants also indicates that the IP is nothing more than
an indirect parameter measuring the reactivity of molecules
towards radical species.
1298
100
Decomposition efficiency (%)
90
80
FA
70 Benzene
Toluene
Styrene
60 o-Xylene
m-Xylene
p-Xylene
12 8 9 10 11 12
Ionization potential (eV)
Figure 10. The relationship between the IP of VOCs and the
decomposition efficiency. The concentrations of VOCs are the same
as in figure 4. The SIE was 85 J L−1 .
The dependence of the decomposition of VOCs on their
IPs in the PDC reactor is shown in figure 10. The IP of the
tested VOCs are in the following order: HCOOH (11.0 eV) >
benzene (9.6 eV) > toluene (8.82 eV) > m-xylene (8.56 eV) >
o-xylene (8.58 eV) > styrene (8.47 eV) > p-xylene (8.44 eV).
However, no correlation of the IP with the decomposition
efficiency was observed for the VOCs tested in this study.
In contrast to the previous studies listed above, formic acid,
which has the highest IP, showed the highest decomposition
efficiency and CO2 selectivity as well. Benzene has a larger IP
than that of toluene. However, the decomposition efficiency
of benzene is slightly higher than that of toluene. Besides
the zero-order decomposition kinetics with the PDC reactor
(see figure 4), these trends of the IP versus decomposition
efficiency also demonstrated that the PDC reactor has a
different decomposition mechanism compared to those of
conventional gas-phase NTP reactors.
3.6. Continuous operation tests
As far as a catalyst is concerned for a chemical reaction,
deterioration of catalytic activity (i.e. durability) should be
taken into account. Continuous operation tests over 150 h
have been conducted to validate the durability of the PDC
system for VOC decomposition. Figure 11 illustrates the
results of long-term operation of the PDC system for the
decomposition of benzene and toluene over 150 h. As was
expected from the good carbon balance with the PDC reactor,
no deactivation of catalytic activity was observed for both
benzene and toluene. The average decomposition efficiencies
for benzene and toluene were 96% and 91%, respectively.
These are quite promising results for the industrial application
of the PDC system.
Figure 12 shows the FE-SEM photos of clean and used
Ag/TiO2 catalysts for benzene decomposition over about
50 h. The used catalyst sample was taken after the long-term
experiment shown in figure 11. Formation of submicrometre-
sized particles was observed on the used catalyst. However,
these aerosols seem to be minor parts of the decomposed
benzene because of the stable performance in the subsequent
operation for 100 h and the good carbon balance as well.
 Decomposition of dilute aromatic compounds

100 investigated using the PDC reactor in this study. The main
findings can be summarized as follows:
Decomposition efficiency (%)

80 (1) The decomposition of VOCs was found to be dependent

on the SIE rather than the gas residence time in the PDC
60 Benzene (100 ppmv) system. GHSV does not affect the VOC conversion using
Toluene (103 ppmv) the PDC system.
(2) Except for styrene, the decomposition of VOCs in the
40
PDC reaction showed zero-order kinetics, which indicated
the important role of the catalytic reaction in the PDC
20 system. The simple kinetic model derived for the VOC
decomposition in the PDC reactor agreed well with the
0 experimental data. The energy constants kE were derived
0 30 60 90 120 150 from the experimental data.
Time on stream (h) (3) The main decomposition products of aromatic compounds
were CO and CO2 . The decomposition of formic acid,
Figure 11. Continuous operation tests of the PDC system for the which is a common intermediate for aromatic compounds,
decomposition of benzene and toluene (SIE = 120–130 J L−1 ).
produced only CO2 (100% selectivity). The selectivities
of CO2 for the tested VOCs showed similar values at
(a) Clean catalyst 71–75% regardless of the type of aromatic compounds
or the SIE.
(4) In contrast to the BaTiO3 packed-bed and gas-phase
capillary discharge plasmas, decomposition of VOCs in
the PDC reactor showed no correlations to the IP of VOCs.
Formic acid, which has the highest IP, showed the highest
decomposition efficiency among the six tested VOCs.
(5) Continuous operation tests over 150 h showed stable
performance without any catalyst deactivation for the
decomposition of benzene and toluene.

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(b) After 50h operation
Figure 12. Field emission type SEM photo for (a) clean Ag/TiO2
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operation of the PDC reactor at high SIE conditions can reduce
the accumulation of particles.
4. Conclusions
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