3B2v8:06a=w ðDec 5 2003Þ:51c Prod:Type:FTP ED:SreejaGA

þ model
EGY : 1664 pp:1210ðcol:fig::NILÞ PAGN:CSR SCAN:global

ARTICLE IN PRESS

3
Energy ] (]]]]) ]]]–]]]
www.elsevier.com/locate/energy
5

7
Effect of additive gases on methane conversion using gliding arc
9
discharge
11
Antonius Indarto, Jae-Wook Choi, Hwaung Lee, Hyung Keun Song
13
Korea Institute of Science & Technology, Clean Technology Research Center, P.O. Box 131, Cheongryang, Seoul 130-650, Korea

F
15 Received 16 November 2004

O
17

O
19 Abstract

PR
Methane conversion using gliding arc plasma has been studied. The process was conducted at atmospheric pressure.
21 Four kinds of additives gases—helium, argon, nitrogen, and CO2—were used to investigate their effects on methane
conversion, as well as products selectivity, and discharged power. Methane conversion was increased with the increasing
23 concentration of helium, argon, and nitrogen in the feed gas but decreased when CO2 concentration increased.
Qualitatively, hydrogen and acetylene were the major gas products. No liquid product was produced.
D
25 r 2005 Elsevier Ltd. All rights reserved.
TE

27 Keywords: Methane conversion; Plasma; Gliding arc discharge; Additive gas

29
EC

1. Introduction
31
The conversion of methane into more valuable compounds, such as hydrogen, synthesis gas, acetylene, and
33 other higher hydrocarbon or black carbon is still becoming a challenge [1]. Many studies have been done
R

intensively for several decades especially for direct methane conversion. The major problem on this route came
35 from the strong C–H bond of methane.
R

Many research groups used the catalytic method to overcome this problem. Although they reported some
37 good results, some problems were found also. Carbon solid deposition on catalyst surface that was produced
O

by chemical reaction became the greatest barrier to transfer this technology from the laboratory to the
39 industrial scale. The catalyst was needed a specific temperature which was usually 100–200 1C higher than
C

room temperature to activate the catalytic site. It means heat supply was significantly required. Another
41 reported problem was the small flow of injected raw gas.
N

Currently, more and more investigations have been deeply performed using non-conventional technology,
43 like plasma technology. Plasmas, both thermal and non-thermal plasmas, have been extensively studied for
U

methane conversion. Different kinds of plasmas and operation conditions produced different product
45 distribution. This characteristic made it suitable for chemical synthesis selection. Methane utilization using
glow discharge [2–4], dielectric barrier discharge (DBD) [5–11], Corona [3,12], Spark [3], arc plasma-jet [13],
47
Corresponding author. Tel./fax: +82 19 352 1981.
49 E-mail address: indarto_antonius@yahoo.com (A. Indarto).

51 0360-5442/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2005.10.034
 EGY : 1664
ARTICLE IN PRESS
2 A. Indarto et al. / Energy ] (]]]]) ]]]–]]]

1 radio frequency (RF) plasma [14,15], thermal plasma [16,17] have been investigated as well as the influence of
additive gases effect. Other plasma variables effect on CH4 plasma reactions such as a plasma power generator
3 [18,19], catalyst process-assisted [20,21], water vapor injection [22] were also experimentally investigated.
Cold plasmas such as corona, glow discharge, and DBD were very cheap and easy to handle, making them a
5 promising possibility to be applied in industry. The main problem was the plasma density which is very low. It
made it rather difficult to achieve a higher conversion at a higher flow rate. However, hot plasmas which
7 typically high temperature arc plasmas produced very high density of plasma and capable to maintain high
injection gas flow rate. But the instrument cost was very expensive and it used more power.
9 To overcome these problems, plasma devices which are located in the transition region between the glow
and arc state ware introduced. Gliding arc plasma at low current intensity, which is also called glowing arc,
11 became a favor due to its characteristics under transition region, such as higher electron density, higher flame
overheating, and high injection flow rate. Its applications have been increasing. Decomposition of H2S [23],
13 N2O [24], CHCl3 and CCl4 [25,26], which were employing gliding arc as the destruction tool, have been
investigated and studied. High percentage of destruction efficiency has been claimed using this method. Many

F
15 papers were also discussing on the discharge behavior of gliding arc plasma. Theoretical and numerical study
of gliding arc to describe it has been published with showing many mathematical equations [27–31].

O
17 In this study, gliding arc plasma was used to convert methane into higher hydrocarbon like acetylene and
other valuable products such as solid carbon black, hydrogen, and synthesis gas. The investigation was deeply

O
19 concerned on the effect of additive gases such as argon, helium, CO2, and nitrogen to the methane conversion,
product distribution and power consumption.

PR
21

23
2. Experimental setup
D
25
The schematic diagram of experimental setup is shown in Fig. 1. Methane with a purity of 99.97% and
TE

27 additive gases were used as a gas source. The details of each part of the system are described in the following
section.
29
EC

31
vent to 5 Litre
atmosphere
33
R

35 wet test
R

meter FID GC
Carbon Sieve 5A
37
O

TCD GC
SK Carbon
39
C

bubble
41 flow
N

meter
43
U

Plasma
45 Reactor

47 CH4
MFC
49
additive gas
MFC
51
Fig. 1. Experimental setup of methane conversion by gliding arc plasma.
 EGY : 1664
ARTICLE IN PRESS
A. Indarto et al. / Energy ] (]]]]) ]]]–]]] 3

1 2.1. Plasma reactor and power system applied

3 The reactor was made from a quartz-glass tube of inner diameter 450 mm and total volume 0.5 l. The upper
part and bottom of the reactor supplied with a Teflon seal comprising two electrodes made of stainless steel.
5 The electrodes were of length 150 mm. The separation of electrodes in the narrowest section was 1 mm. The
gas mixture was injected between the electrodes through a capillary of inner diameter 0.3 mm. A
7 thermocouple, located 100 mm above the electrode, was provided to measure the outlet gas temperatures.
A high frequency AC power supply (Auto electric, A1831) with a maximum voltage of 10 kV and a maximum
9 current of 100 mA was connected to the electrode of gliding arc to generate plasma. The frequency could be
adjusted from 10 to 20 kHz. Fig. 2 shows typical waveforms of voltage and discharge current obtained in this
11 experiment.

13

F
15 2.2. Input gas

O
17 Injection of methane gas and additive gases were controlled by four calibrated mass flow controllers
(MFCs): Tylan, FC-280S with maximum flow capacity of 20 L/min; 3 Bronkhorst Hi-Flow MFCs, with

O
19 maximum flow capacity of 100, 500, and 1000 mL/min. Total gas flow rate was varied from 1 to 3 L/min. The
mixture composition of the outlet reactor was analyzed before and after plasma operation.

PR
21

23
D
25 Normal Acquire Average Acquire
6000 6000
TE

27
4000 4000

29 2000 2000
Voltage (Volt)

Voltage (Volt)
EC

0 0
31
-2000 -2000
33
R

-4000 -4000

35 -6000 -6000
R

-2e-5 -1e-5 0 1e-5 2e-5 -2e-5 -1e-5 0 1e-5 2e-5

37 Time (second) Time (second)
O

39 2.0 2.0
C

1.5 1.5
41 1.0
N

1.0
Current (Ampere)

Current (Ampere)

0.5 0.5
43
U

0.0 0.0
45 -0.5 -0.5
-1.0 -1.0
47
-1.5 -1.5
49 -2.0 -2.0
-2e-5 -1e-5 0 1e-5 2e-5 -2e-5 -1e-5 0 1e-5 2e-5
Time (second) Time (second)
51
Fig. 2. Typical AC wave form that used in this experiment at frequency of 20 kHz.
 EGY : 1664
ARTICLE IN PRESS
4 A. Indarto et al. / Energy ] (]]]]) ]]]–]]]

1 2.3. Measurement system

3 Two gas chromatographers (GCs) have been used to analyze the quantitative amount of products. The
content of hydrogen, O2, CO, nitrogen, and CO2 in the gas mixture before and after the reaction was
5 determined by a GC–TCD (YoungLin M600D, Column: SK Carbon) and the hydrocarbons by a GC–FID
(Hewlett Packard 5890, Column: Haysep Q). The flow of gases to the GC was measured first by bubble flow
7 meter. To check the expansion of gas, the end of main output line was connected to a wet test meter (Ritter
TG5) to measure the fluctuation of main flow after and before experiment running.
9 The evaluation of system performance, selectivity and conversion, were formulated as
moles of H2 produced
11 Selectivity of H2 ¼
100%, (1)
2
moles of CH4 converted
13 x
moles of Cx Hy produced
Selectivity of Cx Hy ¼
100%, (2)
moles of CH4 converted

F
15
moles of CH4 converted

O
17 Conversion of CH4 ¼
100%. (3)
moles of initial CH4

O
Special case when CO2 was used as addictive gas, the formulation would be
19
moles of O2 produced

PR
Selectivity of O2 ¼
100%, (4)
21 moles of CO2 converted

23 x
moles of Cx Hy produced
Selectivity of Cx Hy ¼
100%, (5)
moles of CH4 converted þ moles of CO2 converted
D
25
moles of CO2 converted
Conversion of CO2 ¼
100%. (6)
TE

27 moles of initial CO2

The wave form of voltage and current were captured by oscilloscope (Agilent 54641A) with a high voltage
29 probe (Tektronix 6015A) and a current monitor (Pearson 4997). The amount of power supplied was calculated
EC

by following equation:
31 Z
Power consumption ¼ ðV ðtÞ
IðtÞÞ dt
frequency ðWÞ. (7)
33
R

35
R

3. Results and discussion

37
O

3.1. Pure methane

39
C

Fig. 1 shows the result of pure methane experiment as a function of frequency. In this experiment, total gas
41 flow rate was maintained at 1.5 L/min. It is shown in Fig. 3(a) that the rising of power supply frequency makes
N

conversion of methane become slightly higher. The conversion reaches 40% at 15 kHz and goes up to 45% at
43 20 kHz. Increasing frequency will increase total power that is supplied to plasma reactor. Generally, the power
U

consumption has a linear function to the frequency. Formula 7 is used to calculate the voltage and the current
45 into power as it is shown in Fig. 3(b). The increment of input power will increase energy supply which
probably produce higher dissociation of CH4 molecule and generate more energetic electrons. Song et al. [32]
47 reports one advantage of methane conversion using the gliding arc plasma because of additional heat released
from the plasma reaction. The heat which is produced from the partial oxidation and combustion process of
49 methane conversion in gliding system has to be counted as a significant factor for methane conversion.
Under gliding arc plasma, Methane conversion produces hydrogen, acetylene (C2H2), and carbon (C) solid
51 as the main gas products. The selectivity of hydrogen reaches 40% and acetylene reaches 20%. The rising of
frequency or power did not give a significant effect on product distribution (Fig. 3(c)). The selectivity of
 EGY : 1664
ARTICLE IN PRESS
A. Indarto et al. / Energy ] (]]]]) ]]]–]]] 5

1
60 70

3
50 60
Conversion (%)

Conversion (%)
5
40 50

7
30 40

9
20 30

11 0 0
14 15 16 17 18 19 20 21 100 120 140 160 180 200
(a) Frequency (kHz) (b) Consumed power (Watt)
13
60

F
15

O
50

17
40
Selectivity (%)

O
19 30

PR
21 20

H2
23 10
C2H2
D
0
25 14 15 16 17 18 19 20 21
(c) Frequency (kHz)
TE

27 Fig. 3. Pure methane experiment at total gas flow rate 1 L/min: (a) pure methane conversion as function of frequency; (b) methane
conversion as function of frequency; (c) product selectivity.
29
EC

hydrogen is slightly higher from 35% at 15 kHz to 40% at 20 kHz. However, the selectivity of acetylene is
31 20–22%.

33
R

3.2. Effect of argon and methane gas

35
R

Fig. 4 shows the effect of argon and helium gas to performance of methane conversion at a total gas flow
37 rate of 1 L/min and a frequency of 20 kHz. Generally, argon and helium made a positive effect on methane
O

conversion. The conversion is higher with increasing concentration of these gases (Fig. 4(a)). Comparison
39 between argon and helium, these gases gives almost same characteristic on methane plasma reaction. No
C

significant different between those gases on the product results. Song et al. [33] reports that argon and helium
41 have a meta-stable energy level which could help the dissociation of carbon–hydrogen bond of methane
N

molecule. The existence of meta-stable argon or helium in the plasma system will increase the number of
43 energetic unstable species and increase the possibility to react with methane.
U

In terms of products distribution, Fig. 4(b) shows the selectivity of hydrogen in the product stream gets
45 increase when the concentration of argon or helium (b) is in a higher concentration. On the other hand, the
selectivity of acetylene (C2H2) will be lower at the similar phenomena. It means that increasing concentration
47 of argon or helium makes the plasma reaction tend to produce hydrogen rather than higher hydrocarbon, such
as acetylene. Abundant amount of electrons and excited argon or helium atoms lead the reaction into
49 fragmentation reaction rather than re-arrangement into higher species.
Lower ionization potential of argon and helium affects in decreasing power consumption of methane
51 reforming when those gases are existed in feed stream. Fig. 4(c) shows the consumed power is significantly
decrease from 170 W into 120 W when b has changed from 1 to 0.15.
 EGY : 1664
ARTICLE IN PRESS
6 A. Indarto et al. / Energy ] (]]]]) ]]]–]]]

1 100
80

3 80
H2 selectivity
60
Conversion (%)

Selectivity (%)
5 60

40 Ar
Ar
7 40 He
He
C2H2 selectivity
9 20
20

11 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(a) β=[CH4]/{[additive gas]+[CH4]} (b) β=[CH4]/{[additive gas]+[CH4]}
13
200

F
15

O
Consumed power (Watt)

175
17

O
Ar
150 He
19

PR
21 125

100
23
0
D
25 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(c) β=[CH4]/{[additive gas]+[CH4]}
TE

27
Fig. 4. Methane+argon or helium experiment at total gas flow rate 1 L/min: (a) methane conversion; (b) product selectivity; (c) power
consumption.
29
EC

3.3. Effect of nitrogen gas

31
The effect of nitrogen gas on methane conversion has been studied also. Fig. 5 shows its effect on methane
33
conversion, product selectivity, and power consumption at a total gas flow rate of 1 L/min and a frequency of
R

20 kHz. As shown in Fig. 5(a), the methane conversion increases when the concentration of nitrogen in the
35
mixed gas increases. The increasing rate of methane conversion is started from b ¼ 0:4 and it achieves 65% at
R

b ¼ 0:8. It means that at lower concentration of nitrogen gas, conversion of methane is not significantly
37
O

different and relatively stable. In our previous work, when the concentration of nitrogen was quite low, the
nitrogen molecule was not involved in plasma-chemical reactions, but at higher concentration, it has a high
39
possibility to contribute in the reaction mechanism by excitation of N2 molecules [34]. This excitation of N2
C

into higher vibrational level and meta-stable state (N2(A) and N2(a0 )) will help to increase the conversion of
41
N

methane.
The effect of nitrogen on product selectivity is presented in Fig. 5(b). Increasing concentration of nitrogen in
43
U

the mixed gas will increase the selectivity of hydrogen. In case of acetylene, the selectivity achieves 60% at
b ¼ 0:5 and decreases to 40% at b ¼ 0:2. Compared with Fig. 4(b), the selectivity ratio between H2 and C2H2
45
is lower than that when argon and helium is used as additive gases. Diamy et al. [2–4] have proposed the
kinetic reaction of CH4/N2 on plasma reaction. Compared to Argon and Helium, N2 has more important role
47
to lead the mechanism reaction. The mechanism of reaction would be:
49 CH4 þ N2 ðAÞ ! CH3 þ H; (8)

51
CH4 þ N2 ða0 Þ ! C þ 2H2 ; (9)
 EGY : 1664
ARTICLE IN PRESS
A. Indarto et al. / Energy ] (]]]]) ]]]–]]] 7

1 100
80

3 70
80
Conversion (%)

Selectivity (%)
H2
5 60 60
C2H2

50
7 40

40
9 20
30
11 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
13 (a) β=[CH4]/{[N2]+[CH4]} (b) β=[CH4]/{[N2]+[CH4]}

F
200
15

O
180
Consumed power (Watt)

17

O
160
19

PR
140
21

23 120
D
0
25 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(c) β=[CH4]/{[N2]+[CH4]}
TE

27
Fig. 5. Methane+nitrogen experiment at total gas flow rate 1 L/min: (a) methane conversion; (b) product selectivity; (c) power
consumption.
29
EC

31 C þ CH3 ! C2 H2 þ H; (10)

33 C þ CH2 ! C2 H2 (11)
R

and produces ratio of H2 to C2H2 close to 1:1.

35
The methane conversion reaction goes into a complex reaction when nitrogen is used as an additive gas.
R

Although the dissociation energy of nitrogen is relatively high (higher than dissociation of CH3–H by factor of
37
2), small amount of nitrogen has a possibility to react and produce products that contain N atom, such as
O

HCN, NH3.
39
However, similar to argon and helium, the addition of nitrogen produces lower energy consumption (Fig.
C

5(c)). The power consumption reduces up to 140 W at b ¼ 0:3.

41
N

43 3.4. Effect of CO2 gas

U

45 The addition of CO2 to the methane reaction has been studied to produce the synthesis gas (CO+H2)
[6,10,17]. Before applying CO2 as additive gas on methane reaction, the experiment is done by pure CO2
47 decomposition. Fig. 6 shows the decomposition of CO2 as a function of total gas flow rate from 1.3 to 2.2 L/
min by gliding arc plasma. The conversion is decreasing with increasing total gas flow rate (Fig. 6(a)).
49 Increasing total gas flow rate reduces the resident time of gas inside the reactor and reduce the chance of CO2
to collide with electron or other exited species in the plasma reaction.
51 In case of products selectivity, the main products (Fig. 6(b)) are CO and O2. Calculation of material balance
of oxygen atom from these two compounds achieves more than 80% for all experiment condition. In terms of
 EGY : 1664
ARTICLE IN PRESS
8 A. Indarto et al. / Energy ] (]]]]) ]]]–]]]

1 50
80

3 40
60
Conversion (%)

Selectivity (%)
5 30

40
7 20

9 20
10 CO
O2
11 0 0
1.2 1.4 1.6 1.8 2.0 2.2 2.4 1.2 1.4 1.6 1.8 2.0 2.2 2.4

13 (a) Total gas flow rate (Nl/min) (b) Total gas flow rate (Nl/h)

F
270
15

O
Consumed power (Watt)

255
17

O
240
19
225

PR
21
210

23
195
0
D
25 1.2 1.4 1.6 1.8 2.0 2.2 2.4
(c) Total gas flow rate (Nl/min)
TE

27 Fig. 6. Pure CO2 experiment at frequency 20 kHz: (a) CO2 conversion; (b) product selectivity; (c) power consumption.

29 power consumption (Fig. 6(c)), CO2 treatment requires higher consumed energy than CH4. It can be proposed
EC

because of the chemical bond of C–O in CO2 is much stronger and stable than bond of C–H in CH4.
31 Fig. 7 shows the experiment result of methane conversion which is influenced by CO2 at a total gas flow rate
of 1 L/min and a frequency of 20 kHz. The conversion has a tendency to decrease with increasing
33 concentration of CO2 in the mixed gas (Fig. 7(a)). The conversion drops from 45% at b ¼ 1 to 35% at b ¼ 0:2.
R

In case of CO2, the conversion of CO2 increases with increasing CH4 concentration. The maximum conversion
35 of CO2 reaches 33% at b ¼ 0:9. Different from the previous gases, argon and helium, CO2 is difficult to be
R

transformed into meta-stable state and not giving a positive effect on methane conversion. On the other hand,
37 lower meta-stable level of CH4 makes the existence of CH4 in the plasma reaction increase decomposition
O

efficiency of CO2.
39 Although it produces negative effect on the methane conversion, existing CO2 in the mixed gas has an
C

important role to govern the distribution of products (Fig. 7(b)). The selectivity of hydrogen was down to 40%
41 at b ¼ 0:8 but continuing up to 60% at b ¼ 0:2. It means higher concentration of CO2 would increase the
N

production of H2. Decreasing trend was shown by CO selectivity when the concentration of CO2 decreased. It
43 is caused by reduction of oxygen in the feed gas. Dissociation of CO2 will produce CO and radical O as
U

products. At higher concentration of CO2, more radical O will be produced and give higher possibility to react
45 with CH4

47 CH4 þ O ! CO þ 2H2 : (12)

49 On the other hand, increasing fraction of CH4 will reduce the selectivity of CO (Fig. 7(b)) and the plasma
reaction tents to produce higher hydrocarbon products, such as acetylene.
51 Interesting point of products selectivity is shown at b ¼ 0:7 (Fig. 7(b)). Calculation of material balance at
this point is close to reaction of
 EGY : 1664
ARTICLE IN PRESS
A. Indarto et al. / Energy ] (]]]]) ]]]–]]] 9

1 60 100

3 50 CH4 80
CO2
Conversion (%)

Selectivity (%)
5 40 60

7 30 40
H2
CO
9 20
C2H2
20

11 0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
13 (a) β=[CH4]/{[CO2]+[CH4]} (b) β=[CH4]/{[CO2]+[CH4]}

F
15 320

O
Consumed power (Watt)

17 280

O
240
19
200

PR
21
160

23 120
0
D
25 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(c) β=[CH4]/{[CO2]+[CH4]}
TE

27
Fig. 7. Methane+CO2 experiment at total gas flow rate 1 L/min: (a) methane conversion; (b) product selectivity; (c) power consumption.

29
CO2 þ 3CH4 ! 2CO þ C2 H2 þ 5H2 : (13)
EC

31 At ba0:7, this mechanism reaction is not applicable to the plasma products distribution.
In terms of power consumption, increasing concentration of CO2 increases the power consumption (Fig.
33 7(c)). It because CO2 has a stronger bond than CH4 and require more supplied energy to break the bond.
R

35
R

4. Conclusion
37
O

The effect of additive gases on methane conversion using gliding arc plasma was investigated. Using gliding
arc, pure methane is converted mostly into C solid, hydrogen, and acetylene. Hydrogen selectivity reaches
39
50% and C2H2 around 20–22%. Increasing frequency produces a higher conversion from 40% to 50%
C

when it increases from 15 to 20 kHz. Argon, helium, and nitrogen produce a positive effect on methane
41
N

conversion and reduce the power consumption. The conversion reaches 65% at 10% CH4 diluted with 90%
of argon or helium. Increasing dilute gas ratio produces higher selectivity of hydrogen and reduces the
43
U

selectivity of C2H2.
CO2 is converted into CO and O2 in the gliding arc plasma. Selectivity of CO reaches 50–60% and O2
45
reaches 30–40%. When methane is mixed with CO2, the conversion of methane gets lower. Hydrogen, CO,
and acetylene are the main products of plasma reaction.
47

49 Acknowledgements

51 This study was supported by National Research Laboratory Program of Korea Minister of Science and
Technology.
 EGY : 1664
ARTICLE IN PRESS
10 A. Indarto et al. / Energy ] (]]]]) ]]]–]]]

1 References

3 [1] Lunsford JH. Catalytic conversion of methane to more useful chemicals and fuels: a challenge for 21st century. Catal Today
2000;63:165–74.
[2] Diamy A-M, Hrach R, Hrachova V, Legrand J-C. Influence of C atom concentration for acetylene production in CH4/N2 afterglow.
5 Vacuum 2001;61:403–7.
[3] Legrand JC, Diamy AM, Hrach R, Hrachova V. Kinetic of reaction in CH4/N2 afterglow plasma. Vacuum 1997;48:671–5.
7 [4] Legrand JC, Diamy AM, Hrach R, Hrachova V. Mechanism of methane decomposition in nitrogen afterglow plasma. Vacuum
1999;52:27–32.
[5] Kado S, Sekine Y, Nozaki T, Okazaki K. Diagnosis of atmospheric pressure low temperature plasma and application to high efficient
9
methane conversion. Catal Today 2004;89:47–55.
[6] Zhang Y-P, Li Y, Wang Y, Liu C-J, Eliasson B. Plasma methane conversion in the presence of carbon dioxide using dielectric-barrier
11 discharges. Catal Today 2003;83:101–9.
[7] Hwang B-B, Yeo Y-K, Na B-K. Conversion of CH4 and CO2 to syngas and higher hydrocarbons using dielectric barrier discharge.
13 Korean J Chem Eng Short Commun 2003;20(4):631–4.
[8] Kim S-S, Lee H, Choi J-W, Na B-K, Song HK. Kinetics of the methane decomposition in a dielectric-barrier discharge. J Ind Eng

F
Chem 2003;9(6):787–91.
15 [9] Kim S-S, Lee H, Na B-K, Song HK. Reaction pathways of the methane decomposition in a dielectric-barrier discharge. Korean J

O
Chem Eng 2003;20(5):869–72.
17 [10] Jeong H-K, Kim S-C, Han C, Hwaung L, Song HK, Na B-K. Conversion of methane to higher hydrocarbons in pulsed DC barrier
discharge at atmospheric pressure. Korean J Chem Eng 2001;18(2):196–201.

O
19 [11] Larkin DW, Lobban LL, Mallinson RG. Production of organic oxygenates in the partial oxidation of methane in a silent electric
discharge reactor. Ind Eng Chem Res 2001;40:1594–601.

PR
[12] Liu C, Marafee A, Mallinson R, Lobban L. Methane conversion to higher hydrocarbons in a corona discharge over metal oxide
21 catalysts with OH groups. Appl Catal A: General 1997;164:21–33.
[13] Coltrin ME, Dandy DS. Analysis of diamond growth in subatmospheric dc plasma-gun reactors. J Appl Phys 1993;74(9):5803–20.
23 [14] Savinov SY, Lee H, Song HK, Na B-K. A kinetic study on the conversion of methane to higher hydrocarbons in a radio-frequency
discharge. Korean J Chem Eng 2004;21(3):1–10.
[15] Lee H, Savinov SY, Song HK, Na B-K. Estimation of the methane conversion in a capacitively coupled radio-frequency discharge. J
D
25 Chem Eng Jpn 2001;34(11):1356–65.
[16] Fabry F, Flamant G, Fulcheri L. Carbon black processing by thermal Plasma. Analysis of the particle formation mechanism. Chem
TE

27 Eng Sci 2001;56:2123–32.

[17] Kim KS, Nam JS, Choi SI, Hong SH. Thermal plasma decomposition of methane for production of hydrogen and carbon black. In:
29 Proceedings of the 5th international symposium on pulsed power and plasma applications 2004, pp. 379–85.
[18] Yao S, Nakayama A, Suzuki E. Acetylene and hydrogen from pulsed plasma conversion of methane. Catal. Today 2001;71:219–23.
EC

[19] Song H-K, Lee H, Choi J-W, Na B-K. Effect of electrical pulse forms on the CO2 reforming of methane using atmospheric dielectric
31 barrier discharge. Plasma Chem Plasma Process 2004;24(1):57–71.
[20] Kim S-S, Lee H, Na B-K, Song HK. Plasma-assisted reduction of supported metal catalyst using atmospheric dielectric-barrier
33 discharge. Catal Today 2004;89:193–200.
R

[21] Song HK, Choi J-W, Yue SH, Lee H, Na B-K. Synthesis gas production via dielectric barrier discharge over Ni/g-Al2O3 catalyst.
Catal Today 2004;89:27–33.
35 [22] Hijikata K, Ogawa K, Miyakawa N. Methanol conversion from methane and water vapor by electric discharge (effect of electric
R

discharge process on methane conversion). Heat Transfer Asian Res 1999;28(5):404–17.

37 [23] Dalaine V, Cormier JM, Lefaucheux P. A gliding discharge applied to H2S destruction. J Appl Phys 1998;83(5):2435–41.
O

[24] Krawczyk K, Mlotek M. Combined plasma-catalytic processing of nitrous oxide. Appl Catal B: Environ 2001;30:233–45.
39 [25] Krawczyk K, Ulejczyk B. Decomposition of chloromethanes in gliding discharges. Plasma Chem Plasma Process 2003;23(2):262–81.
C

[26] Krawczyk K, Ulejczyk B. Influence of water vapor on CCl4 and CHCl3 conversion in gliding discharge. Plasma Chem Plasma Process
2004;24(2):155–67.
41 [27] Fridman A, Nester S, Kennedy LA, Saveliev A, Yardimci OM. Gliding arc gas discharge. Prog Energy Combust Sci 1999;25:211–31.
N

[28] Yardimci O-M, Saveliev AV, Fridman AA, Kendedy LA. Thermal and nonthermal regimes of gliding arc discharge in air flow. J
43 Appl Phys 2000;87(4):1632–41.
U

[29] Kuznetsova IV, Kalashnikov NY, Gutsol AF, Fridman AA, Kennedy LA. Effect of ‘‘overshooting’’ in the transitional regimes of the
low-current gliding arc discharge. J Appl Phys 2002;92(8):4231–7.
45 [30] Richard F, Cormier JM, Pellerin S, Chapelle J. Physical study of a gliding arc discharge. J Appl Phys 1996;79(5):2245–50.
[31] Pellerien S, Richard F, Chapelle J, Cornier JM, Musiol K. J Phys D: Appl Phys 2000;33:2407.
47 [32] Song Y-H, Cha M-S, Kim K-T, Kim Y-H, Kim S-J. Comparison study of plasma generation technique for treating pollutant gases.
In: The 5th international symposium on pulsed power and plasma applications, 2004. p. 404–7.
[33] Song HK, Choi J-W, Lee H. Methane conversion in a gliding arc discharge. In: The 5th International Symposium on Pulsed Power
49
and Plasma Applications, 2004. p. 375–8.
[34] Savinov SY, Lee H, Song HK, Na B-K. The effect of vibrational of molecules of plasmachemical reaction involving methane and
51 nitrogen. Plasma Chem Plasma Process 2003;23(1):159–73.