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Plasma-Catalyst Chemical Process Laboratory

Clean Technology Research Center


Korea Institute of Science and Technology
P.O. Box 131, Cheongryang, Seoul 130-650, Korea
-----------------------------------------

November 10, 2004

Professor N. Lior

Editor-in-Chief

School of Engineering and Applied Science

Department of Mechanical Engineering and Applied Mechanics


University of Pennsylvania

297 Towne Building

220 South 33rd Street

Philadelphia, PA 19104-6315

USA

Dear Sir and Editor,

Please fine enclosed five copies of "Effec t of Additi ve Gases on Me th ane


Con vers io n usin g Gl idin g Arc Dis ch ar ge " by Antonius Indarto, Jae-Wook Choi,
Hwaung Lee, and Hyung Keun Song. I would like to have this manuscript reviewed by
the Journal of Energy.
Further communication should be with the first author Antonius Indarto. Please use the
above address or call me at +82-19-352-1981. You may also contact me by email at
indarto_antonius@yahoo.com. Thank you for your consideration.

Sincerely,

Antotonius Indarto
1. Corresponding Author:

Antonius Indarto
Clean Technology Research Center,
Korea Institute of Science & Technology
P.O. Box 131, Cheongryang, Seoul 130-650, Korea
Email: indarto_antonius@yahoo.com
Telp: +82-19-352-1981
Fax: +82-2-958-5209

2. Prime novelty
Complete analysis of methane conversion mixed with four kinds of gases, helium, argon,
nitrogen, and CO2, by gliding arc plasma was done by calculating the conversion of
methane, selectivity of gas product, and power consumption. The experiment was done
at the same parameter condition and compared each other. Actually, no paper wrote
about this kind experiment (effect of additive gas on methane conversion) in gliding arc
plasma. The result explanation was also compared with other plasma system with use
the same kind of gases.
Effec t of Additi ve Gases on Me th ane C on versi on usi ng Glidi ng Arc

Dis ch ar ge

Antonius Indarto† , Jae-Wook Choi, Hwaung Lee and Hyung Keun Song

Korea Institute of Science & Technology, Clean Technology Research Center,

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

Received 16 November 2004

Abstra ct - Methane conversion using gliding arc plasma has been studied. The process

was conducted at atmospheric pressure. Four kinds of additives gases—helium, :

Helium, Aargon, Nnitrogen, 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 concentration of Hhelium, Aargon, and Nnitrogen in

the feed gas, but decreased when CO2 concentration increased. Qualitatively, hydrogen

and acetylene were the major gas products. No liquid product was produced.

Keywords: Methane conversion, plasma, gliding arc discharge, additive gas

Intr oduct io n

The Cconversion of methane into more valuable compounds, such as hydrogen,

† †
* Corresponding author: E-mail:indarto_antonius@yahoo.com, Tel:+82-19-352-1981
synthesis gas, acetylene, and other higher hydrocarbon or black carbon is still

becoming a challenge [1]. Many studies have been done intensively for several

decades, especially for direct methane conversion. The major problem on this route

came from the strong C-H bond of methane.

Many research groups used the catalytic method to overcome this problem and reported

some good results. But it was not still any problem. A (?) Ccarbon solid deposition on a

(?) catalyst surface, which that was produced by a chemical reaction, became the

greatest barrier to transfer this technology from the laboratory intto the industrial

scale. The catalyst was needed a specific temperature, which was usually 100-200oC

higher than room temperature, to activate the catalytic site. It means heat supply was

significantly required. Another reported problem was the small flow of injected raw gas.

Now daysCurrently, more and more investigations have been deeply performed using

non-conventional technology, like plasma technology. Plasmas, both thermal and non-

thermal plasmas, have been extensively studied for methane conversion. Different kinds

of plasmas and operation conditions produced different product 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], RF plasma [14,15], thermal plasma [16,17] have been

investigated as well as the influence of additive gases effect. OAnother plasma

variables effect on CH4 plasma reaction(s)?, such as a plasma power generator [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 promising possibility. It becomes great possibility to be applied

in the 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 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 spent used more higher power consumption.

To overcome theose problems, plasma devices, which areis located in the transition

region between the glow and arc state, wereas introduced. Gliding arc plasma at low

current intensity, which is also called glowing arc, 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], 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 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].

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 concerned on the effect of additive gases

such as argon, helium, CO2, and nitrogen to the methane conversion, product

distribution and power consumption.


2. Expe riment setup

Figure 1

The schematic diagram of experimental setup is shown in figure 1. Methane with a

purity of 99.97% and additive gases were used as source of gas. Details of each part of

the system are described in the next section.

2.1. P la sma re act or a nd ap pl ied power sy stem

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

comprised two electrodes reduced the consumed power. The conversion could reach

~65% at 10% CH4 diluted with 90% of argon or helium. Increasing dilute gas ratio

produced higher selectivity of hydrogen and reduced the selectivity of C2H2.

CO2 was converted to CO and O2 in the gliding arc plasma. Selectivity of CO reached

50-60% and O2 reached 30-40%. When methane was mixed with CO2, the conversion of

methane relatively decreased. Hydrogen, CO, and acetylene were the main products of

plasma reaction.

Ack no wled gements

This study was supported by National Research Laboratory Program of Korea Minister
of Science and Technology.

Reference s

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challenge for 21st century. Catalysis Today 2000; 63: 165-174.
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for acetylene production in CH4/N2 afterglow. Vacuum 2001; 61: 403-407.
[3] Legrand JC, Diamy AM, Hrach R, Hrachova V. Kinetic of reaction in CH4/N2
afterglow plasma. Vacuum 1997; 48: 671-675.
[4] Legrand JC, Diamy AM, Hrach R, Hrachova V. Mechanism of methane
decomposition in nitrogen afterglow plasma. Vacuum 1999; 52: 27-32.
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[8] Kim S-S, Lee H, Choi J-W, Na B-K, Song HK. Kinetics of the methane
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generation technique for treating pollutant gases. Proceedings of the 5th International
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[33] Song HK, Choi J-W, Lee H. Methane conversion in a gliding arc discharge.
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5 L it t r e
v e n t to
a tm o s p h e re

w e t te s t
F ID G C
m e te r C a rb o n S i e v e 5 A

TC D G C
S K C a rb o n

b u b b le
f lo w
m e te r

P la s m a
R e a c to r

CH 4
MFC

a d d itiv e g a s
MFC

Figure 1. Experimental setup of methane conversion by gliding arc plasma


Reviewers Comments

Reviewer 1

p7 – line 11 : “ because the relative low ionisation potential of argon and helium as
compared to other species”
from the handbook, I found:
CH4 = 12.6 eV, Ar = 15,8 eV, He = 24,5 eV and hydrocarbons and related radicals show
ionisation potential around 10 - 11 eV.. so it seems that this sentence is wrong?
Instead of electrons the presence of excited metastable species of Ar and He could
explain the results obtained..

p8 – line 14: about the role of N2: not only high vibrational levels are involved but
probably also excited metastable species N2 (A) and N2 (a’).

p8 - last line: references Diamy et al. correspond to ref [2, 3, 4] not to [2, 5 ,8].

p9 - kinetic scheme: it would be better to indicate the excited states of N2 in reactions


8 and 9 because the ground state of N2 cannot react with CH4.
i.e.
CH4 + N2(A) → CH3 + H + N2 (8)
CH4 + N2(a’) → C + 2H2 + N2 (9)

p9 – line 18: in reference 4 = no CO2 has been added to CH4, it is a product of the
conversion.

p10 - line13: “Different from..…CO2 was much more difficult to be ionised …..
conversion” :
ionisation potential of CO2 = 13.8 eV , lower than that of Ar and He but higher than that
of CH4 so this sentence is not clear?

p10 - line 15: “Oppositely ….. decomposition of CH4”


This sentence is not easily understood.

p9 -11: Effect of CO2 gas:


the role of atomic oxygen formed in the dissociation of CO 2 should be discussed in the
explanation of figure 7;
O atom reacts with hydrocarbons and radicals.

Perhaps the English would be improved, for example:


p2 - line 2 : “ But it….problem. “ = This sentence is not easily understood.
p3 - line 2 : plasma devices which are or plasma device which is .
p4 - line 9 : it is better to use cu rrent than ampe re.
p6 - last paragraph, line 2 : gas p rodu cts not ga ses produ ct.
p10 - line 19: It means , not it meant.

Rec ommenda tio n : publishable paper; requires revisions as indicated.

Reviewer 2

1. The paper is relevant to the scope of ENERGY.


2. This reviewer is unable to judge the originality, never having worked with
electric discharge processes. The proposed additional reviewer has worked
substantially on such processes.
3. The paper is of scientific relevance.
4. The arguments seem reasonable.
5. The reported work seems complete.
6. This reviewer is unable to evaluate the adequacy of acknowledgement of
previous related work.
7. The paper seems well organized in respect of the definition of its objective,
detailed description of the experimental method, and presentation of the results.
However, the English is very poor, especially with regard to syntax. The
authors should get help in correcting the English. This is the reason for
proposing a major revision, prior to publication.

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