Journal of

ELECTROSTATICS
ELSEVIER

Joum~ of Electrostatics35 (1995) 93-101

Low temperature atmospheric pressure discharge plasma processing

for volatile organic compounds
T. Odaa, A. Kumada", K. Tanaka~, T. Takahashi a and S. Masudab
"Department of Electrical Engineering, the University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113, Japan
bMasuda Research Institute,
Kaneyasu-Bld.6, 2-40-11 Hongo, Bunkyo-ku, Tokyo 113, Japan
The 1,000 ppm VOCs (volatile organic compounds) decomposition performance of SPCP
(Surfaced Discharge Induced Plasma Chemical Processing) was studied relating to various carrier
gas effects, plasma exposing methods and others in order to understand the decomposition
mechanisms. In any carrier gas, a direct SPCP can decompose every VOC tested. The efficient
decomposing cartier gases are oxygen, air and nitrogen in that order. However, when the SPCP
treated gasses (air, nitrogen or oxygen) are mixed with contaminated gasses, oxygen seems be
necessary to decompose VOCs. Four new halogenated (chloro-)organic materials are also tested
as contaminants. The maximum decomposition for every contaminant is found to be more than
90 % and the energy efficiency for each contaminant is roughly in the same order.
1.INTRODUCTION
A cylindrical ceramic reactor, with stripe-discharge electrodes on an inner ceramic wall and
an embedded ground electrode in that wall, can generate a strong low temperature non-equilibrium
plasma by applying high frequency high voltage between both electrodes. The plasma may
produce high energy electrons and cause various chemical reactions. One of authors named that
chemical processing Surface Discharge Induced Plasma Chemical Processing (SPCP) j). The initial
aim of the ceramic reactor was as powerful ozonizer. 2) That ozonizer is now used in many fields.
Authors have already reported that SPCP is very effective in decomposing hydrofluorocarbon,
CFC-22 or CFC-113,3) with a high decomposition rate of more than 99% even at low concentration
(100 ppm) in air. SPCP can also decompose other halogenated or other organic compounds
(trichloroethylene, acetone and alcohol) with good decomposition efficiency)) Other halogenated
organic compounds are also decomposed by SPCP with similar performances. Decomposition
mechanisms of such VOCs are examined by changing the gas conditions and UV-light irradiation
effects. The paper describes such test results.
2.EXPERIMENTAL

2.1. Experimental System

The fundamental experimental setup is changed little from that is shown in Fig. 1 where a gas
mixing point after a ceramic reactor and gas mixing space with a low pressure lmercury lamp (UV
0304-3886/95/$09.50 1995 - ElsevierScienceB.V. All fights reserved.
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94

T. Oda et aL /Journal of Electrostatics 35 (1995) 93-101

a gas mixing point after a ceramic

reactor and gas mixing space with
a low pressure lmercury lamp (UV
source) is newly attached. Typical
experimental procedure is as
follows:
a.DIRECT:
plasma processing
after
mixing
(Mixing Point B)
of contami-nated
air (contaminant is exposed to
plasma)
b. INDIRECT: mixing of contaminated air and
plasma processed
clean air at mixing
point A.
c. UV:
power on of a UV
lamp
(UV
irradiation).
The ceramic reactor tested is 10
mm in inner diameter and 115 mm
long driven by a standard power
supply of 5 Khz.
2.2. Sample

(a) cross section of a reactor

It,
~

UV Lump
,~/Mixing Point A ~
m i c
Reactor

Fl0wl I
Mete~t

Flow[
Mete~
L~

MixingTank

Nz

02

Air Tank

(b) total experimental setup

Fig. 1 Schematic diagram of SPCP experimental setup.

Gases

As contaminants, typical organic

materials decomposed are
a.
trichloroethylene: CICH=CCI2, molecular weight: 131.39, specific gravity:l.47, vapor
pressure 60 mmHg at 20.5~C.
b. tetrachloromethane: CCI4, vapor pressure 89.5 mmHg at 20C. (forbidden from 1996)
c.
1,1,1-trichloroethane: CH3CCI3, vapor pressure 100 mmHg at 20C.(forbidden from
1996)
d. 1,2-dichloroethane: CH2CICH2CI, vapor pressure 61 mmHg at 20C.
e. dichloromethane: CH2C12, 349 mmHg at 20~C
f.
acetone: CH3COCH~, molecular weight:58.08, specific gravity:0.79,
vapor pressure:200 mmHg at 22.7C.
A given amount of liquid was sampled by a micro syringe and was injected into a pressurized
tank containing dry compressed air was mixed at up to 6 atmospheric pressure.
2.3. Experimental

Procedures

Two different series of experiments were done as follows.

2.3.1. Decomposition Mechanism

In order to have a good understanding of the decomposition mechanism, an INDIRECT

method was newly tested where the clean air was introduced into the ceramic reactor. After

95

1". Oda et al.IJournal of Electrostatics 35 (1995) 93-101

plasma processing, the clean air was mixed with other VOC-contaminated air at mixing point
A. A small pen-type low pressure mercury lamp (Hamamatsu Photonics, L937-02, input
power: 5W), is inserted in a mixing gas chamber of contaminated gas and processed air shown
in Fig. 1.
Pure nitrogen or pure oxygen gas are also tested as carrier gas in place of clean dry air.
Trichloroethylene and acetone are tested as contaminants and a large difference of
decomposition performance was recognized. Those data were compared with other typical
data obtained by the standard process (DIRECT method).
2.3.2 A New Sample Test

Decomposition performance of four new halogenated organic compounds Co, c, d, and e

in 2.) was tested to know the applicability of SPCP for halogenated organic contaminant
decomposition. Especially, the two which will be forbidden in the near future.
3.RESULTS AND DISCUSSIONS
3.1 DIRECT and INDIRECT Decom-position Tests for Trichloroethylene and Acetone
3.1.1 Trichloroethylene

3.1.1.1 DIRECT and INDIRECT Effects

The decomposition rates of trichloroethylene in air versus discharge elect-tic
power consumption at the reactor are
shown in Figs. 2 and 3. Fig. 2 was
recorded with a low flow rate; that is, a
flow rate
of the
1,000 ppm
trichloroethylene in air at 400 ml/min and
the rate of pure air was 712 ml/min.
In the case of INDIRECT, the time
interval after the plasma processing (gas
flow time from the reactor to the mixing
point A) is 0.24 seconds and the final
concent-ration of the trichloroethylene is
360 ppm. At power consumption of only
1 W, the decomposition rate is already 40
%, but it does not increase at higher
electric power. At a power of more than
10 or 15 W, it decreases drastically to zero
in the case of the INDIRECT method.
This tendency is similar to ozone
generation.
High power causes high
temperature of the reactor wall and the
produced ozone might be decomposed at
high temperature.
FAN in Fig. 2 means
fan cooling of the reactor with cooling
fins.
Cooling by fan increases the
decomposition rate (Fig.3) occurs. In the
case of DIRECT, more than 90 %

"~
;~
g.

100 f ~
80

-"

-"

--,,- :DIRECT
- i - :INDIRECT
-*-:INDIRECT+FAN

60

Ca
~Q)

40

r,~'m''~:a-""~'*'--"

20

",

'

10

:'.

20

----' - 30

Power (W)
Fig.2 Decomposition rate of trichloroethylene
in air for the low flow rate.
~
o
"~.~
~
~"
C~

100
80

~ " i =

40

/: .. ,IY

20

CT
..~-:INDIRECT

- t-. : I N D I R E C T + F A N

10

20

30

Power (W)
Fig.3 Decomposition rate of vichloroethylene in
air for the high flow rate.

96

T. Oda et aL /dournal of Electrostatics 35 (1995) 93-101

o~ 100 F
"~ 80 ~f/:''"
|"

Interval Time
[ ....
"-*-:10cm(0'
24sec)
I
:70cm(l.68sec)

~ 100
~
c~ 80 I

60

20

20

Interval Time ~.-:10cm(0.08sec)

~
w. :70cm(0.56sec)

60

8
~

10

20
Power (W)

30

10

20
Power (W)

30

(a) low flow rate

(b) high flow rate
Fig. 4 Decomposition rate of 1,000 ppm trichloroethylene in air.
decomposition occurs at only 5 W electric power. On the other hand, in Fig.3 at the high
flow rate (1,000 ppm trichloroethylene: 1,172 ml/min and air: 2,000 ml/min, final
concentration: 370 ppm), the time interval is only 0.08 seconds, and the decomposition rate
gradually increases with electric power for DIRECT and an abrupt decrease of the
decomposition rate (the maximum is not so high as that for DIRECT) at high electric power
is not so apparent. A slight FAN effect (a few %) is detected. In the case of fluorocarbon
decomposition, no decomposition was detected by INDIRECT or UV irradiation. 3~
A time interval between the plasma processing and mixing with contaminated gas at point
A, may affect the decomposition rate that was suggested by Yamamoto. ~} Two joint pipes of
different lengths of 0.1 m or 0.7 m between the outlet of the plasma reactor and the mix-ing
point A of two gases was tested to check radical species and their life times. Results are
shown in Figs. 4 (a) and (b) where the time in parenthesis was the elapsed time before mixing.
In the shortest case, the decomposition rate is the largest which is in good agreement with
the normal radical or ozone life time effects. However, the effect of longer time is not
apparent and the results suggest that the ozone in the air created by SPCP may be the main
decomposition source.
100
3.1.1.2 Carrier Gas Dependence
In place of air, pure nitrogen or
:=_
80
oxygen gas was used as the carrier gas.
E
60
Figures 5 and 6 show such results. In
~
40
nitrogen carrier, the DIRECT method can
easily decompose tri-chloroethylene up to
~
20
99%, but no trichloroethylene can be
~
010
20
30
decomposed by INDIRECT at all.
0
Nitrogen radicals or high energy electrons
Power (W)
in the plasma produced by SPCP may
Fig. 5 Decomposition of trichloroethylene in N 2
destroy trichloroethylene. Their life time
for the low flow rate.
may be very small (of millisecond order
) and any (less than a few percent which is the detection limit) decomposition is not detected
by the INDIRECT method.
---- :DIRECT

-iv

:DIRECT+UV

-*-

:INDIRECI+FAN

- n - :INDIRECT+FAN+UV

(-

~ .........

.-X--

X. . . . . . .

3.1.1.3 UV Irradiation Effects

As the mixing cell contains a UV lamp, the UV irradiation effect is also shown in Figs.

97

7". Oda et al./Journal of Electrostatics 35 (1995) 93-101

5 and 6 with the mark UV.

The
decomposition rate of trichloroethylene is
1oo ~
.
.
.
~
more than 95 % for the low flow rate
so
(1,116 ml/min in total) or 65 % for the
high flow rate (3,172 ml/min) with slight
:"
---0-- : D I R E C T
(weak) UV light irradiation without
4o
-.J,. :INDIRECT*FAN
plasma discharge.
The input power of
20
- ~ :INDIRECT+FAN+UV
the low pressure mercury lump ( source as
o
0
calibration) is only 5 W and total UV
0
10
20
3o
light intensity (2553A) may be less than 1
% (30mW); that is, the UV decomposition
Power (W)
effect is much stronger than SPCP energy.
In the oxygen carrier, the UV effect is Fig. 6 Decomposition of trichloroethylene in
oxygen for the high flow rate.
greater and roughly 80 % or 100 %
trichloroethytene are decomposed by the
very weak UV irradiation.
Sometimes,
100
the UV irradiation effects might be
reduced (decomposition rate decreases) by
;~
80
plasma discharge which is assumed to be
~
6o
In'"
-aDIRECT+UV
ozone and temperature effects.
In a
t
..b. INDIRECT+FAN
~
4o
nitrogen carrier, the UV effect is not so
/
- ~- INDIRECTFAN+UV
large and constant; that is, the
N
20
decomposition rate is 20 % for the low
o
~
o
flow rate and 5 % for the
10
20
30
o
high flow rate.
Power (W)
-

.....?oli

3.1.2 Acetone

Fig. 7 Decomposition of acetone in air for the

3.1.2.1 DIRECT and INDIRECT
low flow rate.
The decomposition performance of
acetone in air by DIRECT or INDIRECT
100
SPCP is shown in Fig.7 where only the
:DIRECT
DIRECT method can decompose 90 %
?-2
80 - t v : D I R E C T + U V
t
,
:INDIRECT+FAN
acetone at 30 W for the low flow rate
~ ~ " ~ - - . - ~l
~E 60 - ~ - : I N D I R E C T + F A N + U V. j r ' (1,000 ppm acetone in air:400 ml/min +
dry air:716ml/min).
The maximum
~
4o
decomposition rate by INDIRECT method
~
20
is less than 20 %. For the high flow rate
~
o
(1,000 ppm acetone air: 1172ml/min,
0
10
20
30
air:2,000ml/min), the decomposition
Power (W)
rate is very low and the maximum rate is
only 60 % at 30W by DIRECT shown in Fig. 8 Decomposition of acetone in air for the
Fig.8. For the same high flow, the dehigh flow rate.
composition rate by INDIRECT is roughly
the same as that for the small flow rate, 20 %. All decomposition rates of acetone are much
smaller than rates of trichloroethylene at the same conditions indicating that the decomposition
of acetone is difficult. For the higher flow rate, the maximum decomposition rate is less than
70 % by DIRECT. By gas-chromato-analysis, no apparent difference of processed products

98

T. Oda et al./Yournal of Electrostatics 35 (1995) 93-101

were detected.
100
3.1.2.2 Carrier Gas and UV Effects
When the carrier gas is oxygen, the
decomposition rate of acetone is very
high compared with the air carrier which
is shown in Figs. 9 and 10. Especially,
the maximum decomposition rates of
acetone by INDIRECT are very high, as
60 % for the low flow rate or 40 % for
the high flow rate compared with the
case in air or nitrogen. Ozone or O
should be very effective in decomposing
acetone. The UV irradiation effect is
very small, similar to the air carrier
although UV is very effective in
decomposing trichloroethylene.
The
time interval effect is shown in Fig. 11.
For the high gas flow rate, the
decomposition rate for a short path and
low electrical power is very high at 60
%, but it reduces to the same level for a
long gas pipe when the input electric
power is large. For the low flow rate
of carrier gas, 10 or 20 % higher
decomposition rate (constant to be 60%)
ocurs in most power consumption range.
When the carrier gas is nitrogen, the
decomposition rate of acetone is low.
Compared with the air carrier, the
decomposition rate is 5 or 10 % smaller
by DIRECT shown in Fig. 12 for the low
flow rate. The rate is less than 5 %
(within error level) which is much
smaller than that for the air carrier by
INDIRECT.
Oxidation of acetone
should
be
the
essential
for
decomposition.

:
"~
~~
:~
~
~
~/

80
60
40

["
~

+
-

:DIRECT

:DIRECT+UV
-k. :INDIRECT+FAN

20
0

-~-

10

:INDIRECT+UV+F
AN

20

30

Power (W)
Fig. 9 Acetone decomposition in oxygen for the
low flow rate.
~
o=
:~
~-

100
80
60

.a/"

9<

--x

40
"8
~
"~

20
0

--Jr- : I I ~ C T + F M q
- - :ll~ll~ffr+F.~q+lJV

10

20

30

Power (W)
Fig. 10 Aceton decomposition in oxygen for the
high flow rate.
~

100

:~
~$
:~
~6

80
60

Interval Time
--*-:ll)cm(0.08sec)
m. :70cm(0.56sec)

40
20

)
-0 _r."
2 Four New Halogenated VOCs
0
10
20
30
Figure 13 shows one example of
Power (W)
tetrachloromethane
decomposition
performance versus electric power
Fig. 11 Acetone decomposition in oxygen for
consumption where the residence time is
different mixing time interval.
calculated as the reactor volume divided
by the gas flow rate. A very high decomposition rate of more than 95 % is realized at
electrical power consumption of 30 - 40 W for 1,000 ppm tetrachloromethane in air. When
e,:

99

T. Oda et al.IJournal o f Electrostatics 35 (1995) 93-101

the concentration of contaminant is 100

ppm, the higher decomposition rate
100
o
was recorded.
:~
80
The necessary electric power
consumption to decompose one
60
E
,fi/"
-I- :DIRECT+UV
o
mole of contaminants is shown in
J
--~,- :INDIRECT
40
Fig.14 where original contami-nant
?
R E-, ~_......
.-,:I.NDI
._
CI+U V
concentration for each of tetraethane,
20
trichloroethane, di-chloroethane or
0
dichloro-methane, is 1,000 ppm. In
10
20
30
0
every case, the minimum power is 2 Power(W)
3 X 10 7 J/mole order. However, the
decomposed product analysis6) suggests
Fig. 12 Acetone decomposition in nitrogen for the
that there are many intermediate bylow flow rate.
products includ-ing poisonous materials
when the decomposition rate is less
than 60 or 70 %. In general, when the
100
at

g
flow rate is large (small residence
0
/
m'"
:.
2_80
,.
.,time), the necessary power to
decompose one mole of VOC is small.
60
E
i ,
Residence Time
At the decomposition
o
--*- :0.39s
40 ; ..
rate of 80 %, dichloroethane is the
;"
"--:0.76s
;.
easiest decomposed among four VOCs
20
--- : 1.65s
and trichloroethane is the most stable
0
(the most difficult material to
10
20
30
40
decompose). However, the difference
is only factor of 2 or 3. At the high
Power (W)
decomposition rate, NzO increases in
(a) 100 ppm
the product gases.
4.CONCLUSIONS
SPCP decomposition performance
of 1,000 ppm volatile organic
compounds )VOCs) in atmospheric
pressure air, oxygen or nitrogen was
tested.
Oxygen is found to be the
most destructive carrier gas of dilute
VOCs. VOCs in pure nitrogen carrier,
especially trichloroethylene, can be
decomposed by SPCP when the
contaminated gas is directly processed.
However, the VOCs decomposition
performance by the INDIRECT metkod
(plasma processed nitrogen gas is
mixed with contaminated gas), is very
poor indicating the life-time of the

"~
.~
"8
-~
E
8
c3
"~

100
80

~ A _ , _ . A- . . . . . . . . .
m#

60

, /
A

A'.-i ......

, .."
.-""

/ J"

" " ~ T i m e

t'" J

40

---:0.39s

i~" J
~/

20

.l,--

.... :0.76s
-"- : 1.65s

10

20

30

40

Power (W)
(b) 1,000 ppm
Fig. 13 Decomposition of tetrachloromethane for
100 and 1,000 ppm in air by SPCP.

1O0

T. Oda et al./Journalof Electrostatics 35 (1995) 93-101

nitrogen radical or high energy electron produced by the plasma which may decompose VOCs
is assumed to be very small. Ozone or O radical seems to be very effective in decomposing
VOCs as opposed to the fluorocarbon decomposition test (where no decomposition was found
by the INDIRECT method).
For all 1,000 ppm chloro-organic compounds in air
(tetrachloromethane, trichloroethane, dichloroethane or dichloromethane), the necessary electric
power to decompose 1 mole of VOCs is found to be 2 - 3 X 107 J/mole when the
decomposition rate is 60 or 70 %.
Trichloroethylene was found to decompose with a slight irradiation of UV light, but the
mechanism is not yet understood.
Much further research should be done for further practical application of SPCP gas control.
REFERENCES

1)
2)
3)
4)

5)
6)

S.Masuda "Non-Equilibrium Plasma Chemical Process PPCP and SPCP for Control of
NOx, Sox and Other Gaseous Pollutants," Proc.4th Int.Conf.ESP pp.615-623(1990)
S.Masuda et al, "A Ceramic-Biased Ozonizer Using High Frequency Surface Discharge,"
IEEE Trans. IA-24, pp.223-231(1988)
T.Oda et al, "Atmospheric Pressure Discharge Plasma Processing for Gaseous Air
Contaminants," IEEE Trans. IA-29, pp.787-792(1993)
T.Oda et al, "Decomposition of Gaseous Organic Contaminants by Surface Discharge
Induced Plasma Chemical Processing - SPCP," Conf.Rec.of IEEE/IAS 1992 Ann.
Meeting pp. 1570-1574(1992).
T.Yamamoto:private communication.
to be presented in future Conference.

101

T. Oda et al./Journal o f Electrostatics 35 (1995) 93-101

~18
Resi.dence Time ---*-:0.39s

o E 16
~

14

12

~:

10

o x
~
12

u~

~ )

,!

~.=__ 10

.~
Z

~t

~.o

Residence Time
- * - :0.39s
.m. :0.76s
-~-:l.65s

~16

"'~" :0.76s
-~-:1.65s

~,~ .....

..A

." ak

~.~ 6
E o

-"

20

40

60

80

100

Rate of Decomposition (%)

(a) tetrachloromethane

16
14

12

~0

- ~ - :1.65s

_
o

100

,..i

10
f
/

._=

.g~ 6
o

i/ ,!A1

- ~- :1.65s

~12

"

/' .'"
/~)'li"" .an

ud

80

Residence
Time
~ - :0.39s
"'~" :0.76s

~ 14
/,
!
!
!
!

/'

60

18

Residence Time ~ - :0:39s

"'~" :0.76s

8
~.~

40

(b) trichloroethane

o-6
o-,

20

Rate of Decomposition (%)

~ . ~o 2

~ ..~~ 0
e~

'

20

40

60

80

Rate o f Decomposition (%)

.-

100 :'.~' ~
~ ~

20

40

60

80

Rate of Decomposition (%)

(c) 1,2 dichloroethane

(d)di-chloromethane
Fig. 14 Necessary electrical energy to decompose 1 mole VOCs in air where
concentration is 1,000 ppm.

100