Pilot-Scale NOx and SOx Removal from Boiler

Emission Using Indirect Plasma and Chemical Hybrid

Process
Toshiaki YAMAMOTO, Hidekatsu FUJISHIMA, Masaaki OKUBO and Tomoyuki KUROKI
Department of Mechanical Engineering, Osaka Prefecture University
1-1 Gakuen-cho, Sakai, Osaka 599-8531 JAPAN
E-mail: yamamoto@me.osakafu-u.ac.jp
Abstract The pilot-scale simultaneous NOx and SOx removal
from boiler emission was performed using an indirect plasma
and a chemical hybrid process. The flue gas flow rate was in the
range of 450~1,470 Nm3/hr, the gas temperature of 280oC, and
NOx concentration of 30 ppm for city gas firing, and 70 ppm of
NOx and 35 ppm of SOx for heavy oil firing, respectively. The
radical injection by the indirect plasma was demonstrated to be
extremely effective for NO oxidation especially when the flue gas
temperature is in the range of 300oC where NOx is generated at
this temperature. The produced NO2 was further reduced to N2
and nontoxic and water soluble Na2SO4 by Na2SO3 chemical
scrubber. For the case of oil firing boiler SO2 was simultaenously
adsorbed by NaOH solution. The NOx removal efficiency for gas
firing exceeds 90% but NOx removal efficiency for oil firing was
in the range of 60% due to the lack of ozone concentration with
the present pulse power supply. The removal efficiency of SO2
was in the range of 85~90%. The NOx removal efficiency was
evaluated by the ratio of the radical flow rate by the indirect
plasma to the primary flue gas flow rate, specific energy density,
and Na2SO3 concentration and chemical flow rate. Finally, the
quality of disposed water was investigated and proved to be
disposable.
Keywords- Nonthermal plasma; Remote plamsa; Indirect
plasma; NOx and SOx removal; Hybrid process

I.

INTRODUCTION

The laboratory-scale nonthermal plasma-chemical hybrid

process for simultaneous NOx and SOx removal has been
investigated over the years and demonstrated to achieve a
nearly complete NOx and SOx removal with negligible
reaction byproducts [1-5]. The operating cost was less than 1/4
of the conventional selective catalytic reduction (SCR) system.
Based on the laboratory-scale experimental studies, the pilotscale NOx and SOx removal from boiler emission was carried
out using an indirect plasma and a chemical hybrid process.
The flue gas flow rate was in the range of 450~1,470 Nm3/hr,
the gas temperature of 280oC, and NOx concentration of 30
ppm for city gas firing, and 70 ppm of NOx and 35 ppm of
SOx for oil firing, respectively. The indirect plasma (or often
referred to as remote plasma) means that air radicals are
externally produced at ambient temperature and pressure, and
injected into the hot flue gas. It is extremely effective for NO
oxidation especially when the flue gas temperature exceeds
300oC where NOx is generated at this temperature [6]. The

IAS 2005

produced NO2 was further reduced by the chemical scrubber to

form N2 and nontoxic and water soluble Na2SO4 with Na2SO3
solution. For the case of oil firing boiler, SO2 was
simultaneously adsorbed by NaOH solution.
The radical injection methods for the purpose of NO
oxidization and reduction have been investigated using ozone
(O3), ammonia (NH3), nitrogen (N2), and methane (CH4) and
N2 mixture in both laboratory-scale and pilot-scale experiments
[7-16]. Zhou et al. [7] have investigated the NOx removal
using NH3 radical injection, which was generated by the
plasma jets uisng NH3, CH4, H2 and their mixtures, at the test
facilities. The results showed that NH3 plasma-injection was
more effective than direct plasma with NH3 mixture in the flue
gas and the maximum of 85 % NOx removal was achieved at
400 W in a small-scale laboratory combustor. Similarly, 85~90
% of NOx removal was achieved at plasma torch power of 1.5
kW in a large-scale combustor. Nishida [8,9] reported that NO
in N2 gas was removed by injecting NH3 radicals, which were
externally generated by NH3 diluted with argon, Ar, through
the dielectric barrier discharge. Similar large-scale experiments
were carried out by Dinelli et al [10] and showed a successful
result. Chang et al. [11] examined the combustion flue gas
NOx removal by the corona discharge activated by CH4 radical
injection using the two types of corona radical injectors, hollow
needle and multi-hollow types at a laboratory-scale setup. The
experimental results showed that NOx removal efficiency
increased with increased voltage and non-monotonically
depended on CH4 stoichiometry. Regarding O3 injection, Sano
et al. [12] and Yoshioka et al. [13] have evaluated NO removal
from diesel vehicle exhaust gas using oxygen injection, HC
addition and direct discharge. It was found that oxygen
injection could remove more NO than the case without oxygen,
but HC addition to the ozonizer deteriorated NO removal
efficiency. Simakev et al. [14] have carried out the ozoneammonia injection for simultaneous SOx and NOx removal of
the flue gas generated from a 200 MW coal fired-boiler. The
gas flow rate was varied at 5,000, 7,000 and 10,000 m3/hr. The
results showed that around 90% of SO2 removal efficiency and
75% of NOx removal efficiency were achieved with optimal
operating mode with flue gas-ozone contact time of 0.45
seconds and with an ozone flow rate of 0.4 g/m3 when the gas
flow rate was 10,000 m3/hr. Some other researchers
investigated ozone injection for NOx removal and showed the
its effectiveness of the indirect plasma method [15,16].

2906

0-7803-9208-6/05/$20.00 2005 IEEE

Our approach is to use the air radical injection and chemical

hybrid process to remove the NOx and SOx, whcich is
effective NO oxidation for the gas temperature in the range of
300oC, where NO oxidation is difficult with direct plasma. The
NOx removal efficiency was evaluated by the ratio of the
indirect plasma flow rate to the primary flue gas flow rate,
specific energy density, and Na2SO3 concentration and
chemical flow rate. Finally, the quality of disposed water was
investigated.
II.

EXPERIMENTAL SETUP

Fig. 1 shows a schematic diagram of the pilot plant facility

of air radical injection and a chemical flue gas treatment
system. Flue gas was generated from the 2.0 ton/hr of steam
generation boiler with firing a city gas (13 A) of 121 Nm3/hr or
heavy oil of 115 kg/hr as the rated values (Takao Tekkou Co.).
The air radicals were generated by the pulse plasma reactor at
atmospheric pressure and temperature and then injected into
280oC flue gas right after of the boiler exit. The flue gas was
cooled down with spraying water in the duct to decrease the
gas temperature low enough for protection of the 1.2 m high
polypropylene packing materials in the scrubber. Then, the gas
entered the 0.9 m in diameter and 5.14 m high scrubber.
Na2SO3 solution as reducing chemical was sprayed from the
top of the scrubber to react with NO2 (2NO2 + 4Na2SO3 4
Na2SO4+ N2) and additional NaOH solution for oil firing was
used. Then, flue gas was discharged to the stack.
The plasma reactor consists of 14 sets of twisted wire
centered in the 0.2 m in diameter and 0.5 m high stainless steel
spiral coil electrode. The ambient air was induced and passed
through the 10 kW pulse generator to produce active species.
The thyristors were used as a high voltage switch to release the
stored energy through the condenser. The magnetic pulse
compression circuit was utilized to produce the sharp rise time

Fig. 1. Schematic diagram of the pilot plant facility of air radical

injection and a chemical flue gas treatment system.

IAS 2005

Fig. 2. Overview of the pilot-scale indirect plasma and chemical

hybrid system.

with extremely short pulse width. The pulse repetition

frequency can be varied up to 1,000 pps (pulse per second). Fig.
2 shows the overview of the pilot-scale indirect plasma and
chemical hybrid system.
The experiments were performed after the gas
temperature reached steady state. The flue gas was based on
20~80% load and was set at 450, 940, and 1,470 Nm3/hr for
gas firing and 660 and 1, 470 Nm3/hr where the gas flow rate
was determined by fuel consumption and O2 concentration. The
flue gas temperature was measured with thermocouples and
read with the digital recorder. The concentrations of gas
constituents (O2, CO, CO2, NO, and NOx) were measured with
a gas analyzer (Shimadzu, NOA-7000, chemiluminescence
NOx analyzer, O2 for zirconia method, and CGT-7000, Infrared
adsorption for CO-CO2 analyzer), and by a gas analyzer
(Horiba, PG-235, chemiluminescence NO analyzer). SOx was
measured in accordance with JIS K 0103 turbidimetric analysis
method, and the particulates concentration with JIS Z 8808
filter paper method. The air radical flow rate was varied from
50 ~ 230 Nm3/hr and measured with a float type flow meter.
The O3 concentration was continuously measured by O3 meter
(Ebara, EG-2001B). The voltage-current waveforms were
measured by an oscilloscope (Tektronix, TDS380P) through
the voltage divider (Tektronix, P6015A) and the current probe.
The liquid samples of the scrubbing solution were extracted
periodically through a valve at the bottom basin of the

2907

0-7803-9208-6/05/$20.00 2005 IEEE

scrubber, and pH of the sample was measured by the pH meter

(Horiba, B-211). After the experiments, the sampled scrubbing
solutions were chemically analyzed to check the dissolved
constituents.
RESULTS AND DISCUSSION

A. NOx removal for the city gas boiler

The flue gas temperatures are 250oC at the boiler outlet (i),
200oC at the scrubber inlet (ii), 170oC at the scrubber outlet (iv)
with cooling water spray and 120oC at (ii) and (iv) without
cooling water spray when the gas flow rate was 995 Nm3/hr.
When the gas flow rate was 1,452 m3/hr, the flue gas
temperature became 290oC at (i), 200oC at (ii), and 180oC at
(iv) without water spray, and 60oC at (iv) with cooling water
spray.
Fig. 5 shows the NO and NOx removal efficiencies (herein-after called, NO and NOx) with city gas firing when the flow
rate of the radical air, Qa, was set at 50, 100, 151, or 238
Nm3/hr and the flow rate of flue gas, Qg, was at either 450, 900
or 1,470 Nm3/hr. The ratio of air radical to flue gas (Qa/Qg) was
in the range of 3.3 to 37.5%. As can be seen from the figure
that NO increased with increased Qa/Qg. When Qa/Qg=10%,
NO was around 83 % on average, and when Qa/Qg=25%, NO
be 90% on average where inlet NO concentration was 24 ppm.
When Qa/Qg was at maximum of 37.5%, NO reaches 95%. On
the other hand, NOx increased with increased Qa/Qg. The data
were rather scattered as compared to NO because it was related
to unstable chemical reaction in the scrubber. The NOx
increased 57%, 78% and 87% on average when Qa/Qg was set
at 10%, 25%, and 37.5%, respectively.
The time-dependent NO, NOx and pH value of Na2SO3
solution with Q g=940 m3N/hr and Qa/Qg=10.5% for 260
minutes operation of the city-gas firing was observed. The NO
concentrations at the scrubber inlet (ii) and outlet (iv) did not
vary but NOx concentration at the scrubber outlet (iv)
increased and pH value at the scrubber bottom decreased from
9.1 to 6.8 as time elapsed. The experimental results indicated
that chemicals should be continuously added to keep the
effectiveness of NO2 reduction because the portion of Na2SO3
solution reacts with oxygen in flue gas: 2Na2SO3 + O2
Na2SO4. Thereafter, one stoichiometric amount of Na2SO3
solution was continuously added to the spraying system of the
scrubber.

IAS 2005

2908

Fig. 3. Energy, voltage and current waveforms for pulse plasma

generator.

100

O3 genarat ion rat e (g/ h)

Fig. 3 shows the waveforms of pulse voltage, current, and

energy at the 1,000 pps, where the peak voltage was 83 kV, the
peak current 355 A, and the rising time 100 nano-seconds (ns).
The energy was measured at every 100 pps and showed 3.28
J/pulse regardless of the pulse frequency. The electrical power
was 3.28 kW at the 1,000 pps, 2.27 kW at 700pps, and 1.32
kW at 400 pps, respectively. The pulse frequency was set at
1,000 pps during whole experiments. Air radicals such as O3,
O, OH, OH2, and N were produced by the plasma generator.
Fig. 4 shows the O3 generation rate (g/h) vs. pulse power for a
given induced air flow rate (Wh/m3). The O3 generation
increased up to 80g/h as the pulse power increased to 3.3
Wh/m3.

90
80
70
60
50
40
30
20
10
0
0

0 .5

1 .5

2 .5

3 .5

4 .5

Power (Wh/ m )
Fig. 4. Ozone production rate by the pulse power.

1 00
N O an d N O x re m oval e fficie n cy (%)

III.

90
80
70
60
50
40

N O
30

N O x

20
10
0
0

10

15

20

25

30

35

40

A ir rad ic al ra tio (Q a / Q g ) (% )

Fig. 5. NO and NOx removal efficiencies vs. air radical ratio (Qa/Qg) in
the city-gas firing.

0-7803-9208-6/05/$20.00 2005 IEEE

The gas temperature at the air radical injection point was in

the range of 55oC to 200oC but did not show a significant
difference on NOx removal. However, the effect of the flue gas
cooled with and without water spray in the flue gas on NO and
NOx was investigated when Qg=450 Nm3/hr and Qa/Qg=37.5%.
The NOx cooled with water spray was higher than that without
water. This was attributed to NO2 dissolution with cooling
water.

N O re m o v al effic ien c y (%)

100

Fig. 6 shows the effect of the specific pulse power density

(Wpa) on NO and NOx when Qa/Qg=24.2% and 36.8%. The
input power was varied by changing the pulse repetition rate
from 400, 700, to 1,000 pps, when Qg=450 Nm3/hr. The Wpa
(Wh/m3) defined here was the ratio of the input power to air
radical flow rate. The NO increased 89.6%, 95.6%, and 95.6%
on average as Wpa increased from 1.3, 2.3, to 3.3 Wh/m3, when
Qa/Qg=24.2%. At the same time, NOx increased 52%, 78%, and
84% on average, respectively. The other data at Qa/Qg=36.8 %
showed the similar trend for the case of Qa/Qg=24.2%,
indicating that NOx removal was clearly dependent on plasma
power.

80
70
60
50

Qg= 450 m3N/h

40

Qg= 900 m3N/h

Qg=1,470 m3N/h

30
20
10
0
0

0.2

0.4

0.6

0.8

1.2

1.4

Specific power density (Wh/m 3)

(a)

N O x re m ova l efficienc y (%)

100

Figs. 7(a)-(b) show NO and NOx vs. specific energy density

based on flue gas, Wpg, for all the experiments when Qg=450,
900 and 1,470 Nm3/hr and Qa/Qg varied from 3.3% to 37.5%.
The NO and NOx increased with increase in Wpg, which is
directly related to amount of air radicals. As shown in Fig. 7(a),
NO were 84%, 90% and 93% on average when Wpg=0.4, 0.8
and 1.2 Wh/m3. The NOx were 62%, 77% and 86% at the same
specific powers, respectively as was shown in Fig. 7(b). The
NO reduction energy efficiency (g-NO/kWh) is expressed as
the ratio of the total amount of NO removal (g-NO) to a 1 kWh
of input power. All experimental data were somewhat scattered
because Qa/Qg varied widely from 6.0% to 37.5%. The NO
removal energy efficiency was around 30 g-NO/kWh with
NO=90% and 50 g-NO/kWh with NO=80%.

90
80
70
60
50
40

Q g= 450 m 3N /h
Q g= 900 m 3N /h
Q g=1,470 m 3N /h

30
20
10
0
0

0.2

0.4

0.6

0.8

1.2

1.4

Specific pow er density (W h/m )

(b)
Fig. 7. NO and NOx removal efficiencies vs. specific power density
to flue gas (a) Specific power density (Wh/m3), (b) Specific power
density (Wh/m3/ppm).

The ratio of the scrubbing solution to the flue gas (L/G) on

NOx was investigated when Qg=450 Nm3/hr, Qa/Qg=37.5% and
scrubbing solution flow rate, L, was varied 5.0, 8.0 and the
maximum 11.0 m3/hr. The NOx was hardly influenced by L/G.

N O an d N O x rem o val effic iency (% )

90

The effect of gas residence time (Rt) through the tower packing
of the scrubber on the amount of NOx removal when Qg=450,
900 and 1,470 Nm3/hr and Qa/Qg=6.0%~37.5%. As Rt
increased, the amount of NOx increased slightly because NO
inlet concentration was in the range of 30 ppm.

1 00
90
80
70
60
50

NO

(Q a/ Q g =2 4.2 % )

40

N O x (Q a /Q g =2 4 .2% )

30

NO

20

N O x (Q a /Q g =3 6 .8% )

(Q a/ Q g =3 6.8 % )

10
0
0

0 .5

1 .5

2 .5

3 .5

S p e c ific p u ls e p o w e r d e n s ity (W h / m )

Fig. 6. NO and NOx removal efficiencies vs. specific pulse power

density at changing pulse repetition when Qa/Qg=24.2 % and 36.8%.

IAS 2005

B. NOx removal for the oil fired-boiler

Fig. 8 shows NO and NOx vs. Qa/Qg when Qa was at 50,
100, 151, or 238 Nm3/hr, and Qg was either 650 or 1,170
Nm3/hr. The Qa/Qg was varied in the range of 2.4% to 23.9%.
When Qa/Qg was 10%, 15%, and 20%, NO increased to 50%,
64%, and 73% on average, respectively and increased further
up to around 80% with Qa/Qg=23.9%. As compared to the
results of the city-gas firing, NO were 20~25% lower because
NO inlet concentration was three times more than those of the
city-gas and O3 concentration was lower for the present pulse
power supply. On the other hand, as Qa/Qg increased, the NOx
increased less than that of NO. This was considered to be
unstable chemical reaction in the scrubber. When Qa/Qg=10%,

2909

0-7803-9208-6/05/$20.00 2005 IEEE

N O an d N O x re m oval e fficie n cy (%)

15%, and 20%, NOx was around 37%, 47%, and 53% on
average, and reached 57% with Qa/Qg=23.9%.

1 00
90
80
70
60
50
40
30

NO

20

NOx

10
0
0

10

15

20

25

30

35

40

A ir radic al ratio (Q a/ Q g) (% )

O u tle t N O c on c e ntratio n (ppm )

Fig. 8. NO and NOx removal efficiencies vs. Qa/Qg for the oil firing.

1 00
90
80

Q g=660 m 3N /h

70

Q g=1170 m 3N /h

60
50
40
30
20
10
0
0

10

15

20

25

30

35

40

45

O 3 concentration (ppm )
(a)

Amount of NO removed (ppm)

100
90

Q g=660 m 3N /h

80

Q g=1170 m 3N /h

70
60
50
40
30
20
10
0
0

10

15

20

25

30

35

40

45

O3 concent rat ion ppm)

(b)
Fig. 9. NO outlet concentration and amount of NO removed
concentration vs. O3 concentration (a) NO concentration, (b) NOx
concentration.

IAS 2005

Figs. 9(a)-(b) show the correlation between NO

concentration at the scrubber outlet (iv) and injected O3
concentration in gas. NO outlet concentration sharply
decreased with increase in O3 concentration regardless of the
gas flow rate. NO outlet concentration decreased from 80 ppm
to 10 ppm when 28 ppm O3 concentration was injected.
However, it was clear that amount of NO removed was more
than the amount of corresponding O3 concentration to oxidize
NO. This was attributed that air radicals was not limited to O3,
but other long life radicals, such as O, N and other excited
species.
The effect of the gas temperature at the injection point on
NO and NO vs. O3 density when Qg=650 Nm3/hr and
Qa/Qg=4.8~23.6%. The NO removal efficiencies measured at
low temperature (55oC) were higher than those at high
temperature (200oC), which were reverse results with the citygas firing. However, the difference of NO removal efficiency
for both cases was not affected. Accordingly, the effect of gas
temperature on NO and NOx was not significant.
Figs. 10(a)-(b) show NO and NOx as a function of the
specified power density (Wpg) for Qg =650, and 1,170 Nm3/hr
and Qa/Qg=2.4%~23.9%. It is clear from Fig. 10(a) that NO
increased rapidly with increasing Wpg regardless of the gas
flow rate. The NO was 60% on average at Wpg=0.4 Wh/m3, and
up to around 80% on average at 0.8 Wh/m3 (equivalent to
Qa/Qg=23.9%). Fig. 10(b) shows that NOx was widely scattered
as compared to the NO, especially in the range of more than
0.3 Wh/m3. This was again caused by the lack of O3 from the
present plasma reactor and unstable chemical reaction in the
scrubber. The NOx was 43% on average at Wpg=0.4 Wh/m3,
and up to around 60% on average at 0.8 Wh/m3. The NO
removal energy efficiency decreased significantly as NO
increased. NO energy efficiency was around 90 g-NO/kWh for
NO=60% and 70 g-NO/kWh for NO=80%, respectively, which
was significantly higher for the city-gas firing.
Fig. 11 compares NO vs. the ratio of air radical to gas
flow rate (Qa/Qg) for both fuels. As can be seen from the figure
NO increased with increased Qa/Qg. The NO for the city-gas
increased moderately with increase in Qa/Qg, but NO for the oil
firing increased sharply. The difference of NO between both
fuels depend on the difference of NO inlet concentration i.e. 30
ppm for the city-gas and 80 ppm for the oil, which was similar
to the laboratory test results. The highest NO removal
efficiency obtained was in the range of 89%~95% at Qa/Qg
=37.5% for the city-gas and 81%~84% at Qa/Qg=23.6% for the
oil. As a result, in order to obtain more than 80% of NO, the
Qa/Qg over 20% was needed for both fuels using for this
plasma device.
Fig. 12 showed that amount of NO removal with
stoichiometric O3 injection was significantly higher, indicating
that NO oxidation takes place more than required O3
concentration. The ratio of NO removal to stoichiometric
amount of O3 was 1.8~2.4 for the oil and 1.2~1.8 for the citygas. The results indicated that air radicals were not limited to
O3, but included others, such as O and N excited species. In

2910

0-7803-9208-6/05/$20.00 2005 IEEE

1 00

N O re m oval efficie ncy (% )

N O re m ov al e fficiency (% )

100
90
80
70

Qg=660 m3N/h

60

Qg=1170 m 3N/h

50
40
30
20
10

90
80
70
O il

50
40
30
20
10
0

0
0

0.2

0.4

0.6

0.8

1.2

1.4

10

20

25

30

35

40

Fig. 11. NO removal efficiency vs. air NO radical ratio (Qa/Qg) for both
fuels.

100
90
Qg=660 m 3N/h

80
70
60
50

N O re m o va l am ou n t (ppm )

Qg=1170 m3N/h

40
30
20
10
0
0

0.2

0.4

0.6

0.8

1.2

1.4

Specific power density (Wh/m 3)

50
40
30
20

G as
O il

10
0

(b)

10

O
Fig. 10. NO and NOx removal efficiencies vs. specific power density.

15

20

25

30

35

40

45

c o n c e n tra tio n (p p m )

Fig. 12. Amount of NO removed vs. O3 when Qa/Qg=6~10%.

addition, the flue gas constituents for both fuels such as

moisture and CO2 were responsible for NO oxidation.

2911

10 0
90

G as

80

N O pen etration (%)

Fig. 13 shows the correlation between the penetration and

the specific power density (Wh/m3/ppm) in which all the
experimental data of both fuels were included. The NO
penetration (1NO) means that the penetrated NO was not
removed by the system and discharged outside. The NO
penetration was 25% on average at 0.01 Wh/m3/ppm in specific
power density, and 10% on average at 0.03 Wh/m3/ppm. This
means that even for the case of the oil firing, NO penetration
was reduced with increase in specific power density. When the
specific power density was 0.035 Wh/m3/ppm, the penetration
was 10%, resulting in 90% of NO removal efficiency. It is
interesting to note that NO penetration of the laboratory results
based on Qg=0.6 Nm3/hr, Qa/Qg=5~40% and NO inlet
concentrations of 300, 500, and 700 ppm, were entirely higher
than those of the pilot scale test results. If we compare both
penetration at 0.04 Wh/m3/ppm, the NO penetration was 40%
in the laboratory test, but only 10% in the pilot test result. In
other words, in order to achieve 80% NO efficiency, the

IAS 2005

15

Air radical ratio (Q a/Q g) (%)

Specific power density (W h/m )

(a)

N O x rem oval efficie nc y (% )

G as

60

O il

70
G as
L ab o ratory

60
50
40
30
20
10
0
0

0 .02

0 .04

0 .06

0 .08

S pe c ific p o w e r d en s ity (W h / m / pp m )

Fig. 13. NO penetration rate vs. specific power density when

Qg=450~1,470 m3N/hr and Qa/Qg=3~37% for both fuels, including the
laboratory test results when Qg=0.6 m3N/hr, Qa/Qg=5~40%, and NO
inlet concentration of 300~700 ppm.

0-7803-9208-6/05/$20.00 2005 IEEE

G a s Q g = 45 0 m 3 N / h

160

O il Q g= 6 65 m 3N / h

140

L ab o . te st, G as
Q g =0 .6 m 3 N /h

10 0

N O x rem o v al e ffic ien c y (% )

N O rem oval energy efficiency

(g-N O /kW h)

180

120
100
80
60
40
20
0

90
80
70
60
50
40

Gas

30

O il

20

La b o.

10
0

10

20

30

40

50

60

70

80

90

1 00

N O rem oval efficiency (%)

0 .01

0.0 2

0 .0 3

0.0 4

0.0 5

0 .06

S pe c ific p ow e r de n sity (W h / m / p pm )

Fig. 14. NO removal efficiency vs. NO removal energy efficiency for

both fuels.

Fig. 15. NOx removal efficiency vs. specific power density for both
fuels when Qg=450~1,470 m3N/hr, and Qa/Qg=3~37%, including the
laboratory test results when Qg=0.3, 0.49 and 0.6 m3N/hr, Qa/Qg=10%,
and NO inlet concentration of 300 ppm.

TABLE I
ANALYTICAL RESULTS OF THE SCRUBBING SOLUTION EXTRACTED FROM THE BOTTOM OF THE SCRUBBER FOR BOTH FUELS.
Unit
pH (-)
BOD (mg/L)
COD (mg/L)
SS (mg/L)
S-Fe (mg/L)
T-N (mg/L)
NO2-N (mg/L)
NO3-N (mg/L)
NH4-N (mg/L)
SO3-2 (mg/L)
SO4-2 (mg/L)
Remarks

Sewage disposal
Analyzed sample
Analysis method
regulation
City-gas (8/2)
Heavy oil (8/3)
7.5 (20oC)
8.5 (20oC)
JIS K0102 12.1
5.8~8.6
84
150
JIS K0102 14.1
300
7
34
JIS K0102 17
<1
<1
JIS K0102 21
300
46
84
JIS K0102 57.2
10
19
34
JIS K0102 45.2
240
3
17
JIS K0101 37.1.1
380
13
10
JIS K0101 37.2.3
1250
625
JIS K010240.1
16000
22000
JIS K010241.3
o
1. The waste water disposal standard is based on the sewage regulation standard
specified manufacturing industry of more than 50 m3/d.

specific powers density of 0.013 Wh/m3/ppm is needed for the

pilot test, but 0.051 Wh/m3/ppm for the laboratory test. The
pilot test result was only a quarter of specific power of the
laboratory test results. The similar trend was observed with
other pilot-scale experiments [5].
Fig.14 shows NO vs. NO removal energy efficiency for the
laboratory test data as well as the pilot test data for both fuels.
The NO removal energy efficiency of the laboratory test was in
the range of 40~60 g-NO/kWh regardless of NO. However,
NO reduction energy efficiency of the pilot tests was
dependent on NO and decreased almost linearly as NO
increased. The energy efficiency was in the range of 50~70 gNO/kWh with NO=80%. It is also shown that the pilot test
results showed less energy in the lower range of NO removal
efficiency, as compared to the laboratory results.

IAS 2005

Waste water
regulation
5.8~8.6
160 (Day ave. 120)
160 (Day ave. 120)
200 (Day ave. 150)
10
120 (Day ave. 60)
of Sakai city for the

Fig. 15 shows NOx vs. the specific power density

(Wh/m3/ppm) for all experimental data when Qa/Qg=3~37% for
both fuels. The laboratory test data were also plotted. The
laboratory test condition was set at Qg=0.3, 0.49 and 0.6
Nm3/hr, Qa/Qg=10% and NO inlet concentrations of 300 ppm.
The laboratory data were very close to the pilot scale data.
Even for the case of the oil fuel firing, NO=80% could be
achieved with the specific power density of 0.045 Wh/m3/ppm.
C. SOx and particulates removal
SOx and particulate removal efficiencies were measured
with Qg=676 Nm3/h, Qa/Qg=15.1% for heavy oil firing of
which sulfer content was 0.082%. The measured SOx
concentration was 35 ppm at the boiler outlet (i), and less than
5 ppm at the scrubber outlet (iv). More than 85.9% of SOx
removal efficiency was attained by the system. On the other

2912

0-7803-9208-6/05/$20.00 2005 IEEE

hand, particulate concentration was 11 mg/Nm3 at the inlet, and

7 mg/Nm3 at the outlet. Particulate removal efficiency was
36.4%, which was better than expected considering extremely
fine particulates and the use of the chemical scrubber.
According to these results, the air radical injection and
chemical hybrid system was confirmed to remove
simultaneously NOx and SOx with some particulates from the
boiler emission.
D. Analytical results of the scrubbing solution
Table I shows the analytical results of the scrubbing
solution extracted from the bottom of the scrubber for both
fuels. The concentration of SO42- for both fuels was
significantly higher than SO32-, NO3- and NO2-. It implies that
SO2 was dissolved in the solution, and Na2SO4, which Na2SO3
reacted with NO2 and O2 in flue gas. The SO32- concentration
showed high for both fuels. The NO3- and NO2- for the oil were
detected higher than that for the city-gas due to NO
concentration in fuel. For industrial application, the regulation
of waste water as well as sewage water should be taken into
consideration and pH, BOD, COD, SS and T-N ions are
important items. The measured data were shown in Table I and
the results were satisfied with the regulation except S-Fe
(soluble ferrous ion), which was caused by the corrosion due to
the scrubber casing made of carbon steel. This issue can be
resolved by using anti-corrosion materials such as stainless
steel. Therefore, the waste solution can be exposed outside of
the plant as a general waste water.

REFERENCES
[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

IV.

SUMMARY

The indirect plasma (air radical) and chemical hybrid

process for boiler emission using the pilot-scale plant to
remove NOx and SOx was successfully demonstrated. The
indirect plasma or air radical injection is effective for not only
high flue gas NO oxidation but reducing the plasma treatment
flue gas, resulting in the reduction of the size of the plasma
reactor. The ratio of NO removal to stoichiometric O3
concentration was 1.2~1.8 for the city-gas firing and 1.8~2.4
for the oil firing. Although O3 is the major NO oxidation
species, air radicals were not limited to O3 but others
constituents such as O, N and other excited species. It is
necessary to increase Qa/Qg to attain the high NO removal
efficiency. More than 20% of the radical flow rate was needed
to obtain 80% of NO removal efficiency with the present
plasma power supply. The removal efficiency of SO2 was in
the range of 85~90%. Scrubbing solution was chemically
analyzed and it is confirmed that the waste solution can be
disposed outside of the plant.

[10]

[11]

[12]

[13]
[14]

[15]

[16]

ACKNOWLEDGMENT

[17]

Authors wish to thank you for Takao Tekkosho Co. and

Oriental Kiden Co. for providing the chemical reactor and
plasma reactor system as well as technical support, and Mr.
Haruna and Fukumoto from the graduate student at Osaka
Prefecture University. Also, this work was partially supported
by Grant-in-Aid for Scientific Research (B) of the Japanese
Society for the Promotion of Science.

IAS 2005

2913

T. Yamamoto, C.L. Yang, Z. Kravets, and M. Beltran, "Plasma-Assisted

Chemical Process for NOx Control," IEEE Transactions on Industry
Applications, Vol. 36, No. 3, pp. 923-927, 2000.
C.L Yang, T. Yamamoto, M. Beltran, and Z. Kravets, Corona-Induced
Chemical Scrubber for the NOx Emission, Environmental Progress,
Vol. 17, No. 3, pp. 183-189, 1998.
T. Yamamoto, M. Okubo, K. Hayakawa, and K. Kitaura, Towards Ideal
NOx Control Technology using a Plasma-Chemical Hybrid Process,
IEEE Transactions on Industry Applications, Vol. 37, No.5, Sept./Oct.
2001, pp. 1492-1498.
T. Kuroki, M. Takahashi, M. Okubo and T. Yamamoto, Single-Stage
Plasma-chemical Process for Particulates, NOx, and SOx Simultaneous
Removal, IEEE Transactions on Industry Applications, Vol. 38, No. 5,
Sept./ Oct. 2002, pp. 1204-1209.
T. Yamamoto, K. Sonoyama, and S. Hosokawa, Emission Control from
Incineration Plant Using Nonthermal Plasma-Chemical Process,
Proceedings of the Third International Symposium on Thermal Plasma
Technology for Pollution Control, Cheju Island, Korea, Apr. 23-27,
(2001) pp. .
T. Yamamoto, B.S. Rajanikanth, M. Okubo, and T. Kuroki,
Performance Evaluation of Nonthermal Plasma Reactors for NO
Oxidation in Diesel Engine Exhaust Gas Treatment. IEEE Transactions
on Industry Applications, Vol. 39, No. 6, Nov./Dec. 2003, pp. 16081613..
Q. Zhou, S.C. Yao, A. Russell, and J. Boyle, Flue Gas NOx Reduction
Using Ammonia Radical Injection, J. Air Waste Manage. Assoc. 42,
Vol. 42, No 9, Sept. (1992), pp. 1193-1197.
M. Nishida, K. Yukimura, S. kambara and T. Maruyama, NOx
Removal Using Ammonia radicals Prepared by Intermittent Dielectric
Barrier Discharge at Atomspheric Pressure, Jpn. J. Appl. Phsy. Vol. 40,
(2001), pp.1114-1117.
M. Nishida, K. Yukimura, S. Kambara and T. Maruyama, Reduction of
Nitigen Oxide in N2 by NH3 Using Intermittent Dielectric Barrier
Discharge, J. Appl. Phys.Vol. 90, No. 6, (2001), pp. 2672-2677.
G. Dinelli, L. Civitano, and M. Rea, Industrial Experiments on Pulsed
Corona Simultaneous Removal of NOx and SO2 from Flue Gas, IEEE
Transactions on Industry Applications, Vol. 26, No. 3, 1990, pp. 535541.
J.S.Chang, K. Urashima, M. Arquillq and T. Ito, Reduction of NOx
from Combustion Flue Gases by Corona Discharge Activated Methane
Radical Injections, Combustion Science and Tech., Vol. 133, (1998),
pp. 31-47..
K. Sano and Y. Yoshioka, Effect of Oxygen Injection and HC Addition
on NO Removability of Ozone Injection method, IEE. J. Trans. Vol.
123, No. 10, (2003), pp. 1030-1035.
Y. Yoshioka, NOx removal for Diesel Engine Exhaust by Ozone
Injection Method, Proc. of ISNPT-3, Korea, S6-4, (2001), pp. 119-124.
V. Yu. Simachev, S.S. Novoselov, V.A. Svetlichnyi, A. F. Gavrilov, M.
V. Gorokhov, V.I.Semenov, V. A. Ryzhikov, V.V. Demchuk, An
Investigation of the Ozone-ammonia method of Simultaneous
Desulphurisation and Denitrification of
Flue Gases when Burning
Donetsk Coals, Thermal Engineering, 35 (3), (1988), pp. 67-70..
S.S. Novoselov, A. F. Gavrilov, V. Yu. Simachev, and V.A. Svetlichnyi,
Ozone method of SO2 and NO2 from the flue gas of thermal power
stations, Thermal Engineering, 33, (1986), pp. 496-499.
S. M. Slator and M. S. Rizzone, Simultaneous oxidation of SO2 and
NO in flue gases by ozone injection, Fuel, Vol.59, (1980), pp.897-899
H. Fujishima, Ph.D. Dissertation at the Osaka Prefecture University,
March 2005.

0-7803-9208-6/05/$20.00 2005 IEEE