Professional Documents
Culture Documents
Dis ch ar ge
Anto nius Indart o, Jae-Woo k Choi , Hwau ng Lee and Hyun g Keun Son g
Abstra ct - Methane conversion using gliding arc plasma has been studied. The process
well as products selectivity, and discharged power. Methane conversion was increased
with the increasing concentration of helium, argon, and nitrogen in the feed gas but
Intr oduct io n
The conversion of methane into more valuable compounds, such as hydrogen, synthesis
1
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
Many research groups used the catalytic method to overcome this problem. Although
they reported some good results, some problems were found also. Carbon solid
deposition on catalyst surface that was produced by chemical reaction became the
greatest barrier to transfer this technology from the laboratory to 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.
Currently, 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
using glow discharge [2-4], Dielectric Barrier Discharge (DBD) [5-11], Corona [3,12],
Spark [3], arc plasma-jet [13], 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
[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
2
handle, making them a 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 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.
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, 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
3
The schematic diagram of experimental setup is shown in figure 1. Methane with a
purity of 99.97% and additive gases were used as a gas source. The details of each part
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. 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
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
electrode of gliding arc to generate plasma. The frequency could be adjusted from 10 to
20 kHz. Figure 2 shows typical waveforms of voltage and discharge current obtained in
this experiment.
2.2. In put g as
4
Injection of methane gas and additive gases were controlled by four calibrated Mass
Flow Controllers (MFC): Tylan, FC-280S with maximum flow capacity of 20 L/min; 3
Bronkhorst Hi-Flow MFCs, with 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
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 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 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.
The evaluation of system performance, selectivity and conversion, were formulated as:
moles of H 2 produced
Selectivity of H 2 = × 100%
2 × moles of CH 4 converted (1)
x × moles of C x H y produced
Selectivity of C x H y = × 100% (2)
moles of CH 4 converted
moles of CH 4 converted
Conversion of CH 4 = × 100% (3)
moles of initial CH 4
5
Special case when CO2 was used as addictive gas, the formulation would be:
moles of O2 produced
Selectivity of O2 = × 100% (4)
moles of CO2 converted
x × moles of C x H y produced
Selectivity of C x H y = × 100% (5)
moles of CH 4 converted + moles of CO2 converted
The wave form of voltage and current were captured by oscilloscope (Agilent 54641A)
with a high voltage probe (Tektronix 6015A) and a current monitor (Pearson 4997). The
this experiment, total gas flow rate was maintained at 1.5 L/min. It is shown in figure 3a
that the rising of power supply frequency makes conversion of methane become slightly
higher. The conversion reaches 40% at 15 kHz and goes up to 45% at 20 kHz.
Increasing frequency will increase total power that is supplied to plasma reactor.
Generally, the power consumption has a linear function to the frequency. Formula 7 is
6
used to calculate the voltage and the current into power as it is shown in figure 3b. 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 reports
one advantage of methane conversion using the gliding arc plasma because of additional
heat released from the plasma reaction [32]. The heat which is produced from the
partial oxidation and combustion process of methane conversion in gliding system has
Under gliding arc plasma, Methane conversion produces hydrogen, acetylene (C2H2),
and carbon (C) solid 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 (figure 3c). The selectivity of hydrogen is slightly higher
from 35% at 15 kHz to 40% at 20 kHz. However, the selectivity of acetylene is 20-22%.
Figure 4 shows the effect of argon and helium gas to performance of methane
conversion at a total gas flow rate of 1 L/min and a frequency of 20 kHz. Generally,
argon and helium made a positive effect on methane conversion. The conversion is
higher with increasing concentration of these gases (figure 4a). Comparison between
argon and helium, these gases gives almost same characteristic on methane plasma
reaction. No significant different between those gases on the product results. Song et al
7
reports that argon and helium have a meta-stable energy level which could help the
meta-stable argon or helium in the plasma system will increase the number of energetic
product stream gets increase when the concentration of argon or helium (β) is in a
higher concentration. On the other hand, the selectivity of acetylene (C2H2) will be
helium makes the plasma reaction tend to produce hydrogen rather than higher
helium atoms lead the reaction into fragmentation reaction rather than re-arrangement
Lower ionization potential of argon and helium affects in decreasing power consumption
of methane reforming when those gases are existed in feed stream. Figure 4c shows
the consumed power is significantly decrease from 170 Watt into 120 Watt when β has
The effect of nitrogen gas on methane conversion has been studied also. Figure 5
shows its effect on methane conversion, product selectivity, and power consumption at
a total gas flow rate of 1 L/min and a frequency of 20 kHz. As shown in figure 5a, the
8
methane conversion increases when the concentration of nitrogen in the mixed gas
increases. The increasing rate of methane conversion is started from β=0.4 and it
achieves 65% at β=0.8. It means that at lower concentration of nitrogen gas, conversion
of methane is not significantly different and relatively stable. In our previous work,
when the concentration of nitrogen was quite low, the nitrogen molecule was not
This excitation of N2 into higher vibrational level and meta-stable state (N2(A) and
concentration of nitrogen in the mixed gas will increase the selectivity of hydrogen. In
case of acetylene, the selectivity achieves 60% at β=0.5 and decreases to 40% at β=0.2.
Compared with figure 4b, the selectivity ratio between H2 to C2H2 is lower than that
when argon and helium is used as additive gases. Diamy et. al. has proposed the kinetic
reaction of CH4/N2 on plasma reaction [2-4]. Compared to Argon and Helium, N2 has
more important role to lead the mechanism reaction. The mechanism of reaction would
be:
CH 4 + N 2 ( A) → CH 3 + H (8)
CH 4 + N 2 (a' ) → C + 2 H 2 (9)
C + CH 3 → C 2 H 2 + H (10)
C + CH 2 → C 2 H 2 (11)
9
The methane conversion reaction goes into a complex reaction when nitrogen is used
(higher than dissociation of CH3-H by factor of 2), small amount of nitrogen has a
possibility to react and produce products that contain N atom, such as HCN, NH3.
However, similar to argon and helium, the addition of nitrogen produces lower energy
consumption (figure 5c). The power consumption reduces up to 140 Watt at β=0.3.
3.4. Effec t of CO 2 G as
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
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 (figure 6a). 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.
In case of products selectivity, the main products (figure 6b) are CO and O2. Calculation
of material balance of oxygen atom from these two compounds achieves more than 80%
for all experiment condition. In term of power consumption (figure 6c), CO2 treatment
requires higher consumed energy than CH4. It can be proposed because of the chemical
bond of C-O in CO2 is much stronger and stable than bond of C-H in CH4.
10
Figure 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 concentration of CO2 in the mixed gas (figure 7a).
The conversion drops from 45% at β=1 to 35% at β=0.2. In case of CO2, the conversion
of CO2 increases with increasing CH4 concentration. The maximum conversion of CO2
reaches 33% at β=0.9. Different from the previous gases, argon and helium, CO2 is
difficult to be transformed into meta-stable state and not giving a positive effect on
methane conversion. On the other hand, lower meta-stable level of CH4 makes the
Although it produces negative effect on the methane conversion, existing CO2 in the
mixed gas has an important role to govern the distribution of products (figure 7b). The
selectivity of hydrogen was down to 40% at β=0.8 but continuing up to 60% at β=0.2. It
means higher concentration of CO2 would increase the production of H2. Decreasing
caused by reduction of oxygen in the feed gas. Dissociation of CO2 will produce CO and
CH 4 + O → CO + 2H 2 (12)
On the other hand, increasing fraction of CH4 will reduce the selectivity of CO (figure
7b) and the plasma reaction tents to produce higher hydrocarbon products, such as
acetylene.
11
Interesting point of products selectivity is shown at β=0.7 (figure 7b). Calculation of
At β≠0.7, this mechanism reaction is not applicable to the plasma products distribution.
consumption (figure 7c). It because CO2 has a stronger bond than CH4 and require more
4. Co nc lusi on
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 50% and C2H2 around 20-22%.
increases from 15 kHz to 20 kHz. Argon, helium, and nitrogen produce a positive effect
on methane conversion and reduce the power consumption. The conversion reaches
~65% at 10% CH4 diluted with 90% of argon or helium. Increasing dilute gas ratio
CO2 is converted into CO and O2 in the gliding arc plasma. Selectivity of CO reaches 50-
60% and O2 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.
12
Ack no wled gements
This study was supported by National Research Laboratory Program of Korea Minister
Reference s
[1] Lunsford JH. Catalytic conversion of methane to more useful chemicals and fuels: a
challenge for 21st century. Catalysis Today 2000; 63: 165-174.
[2] Diamy A-M, Hrach R, Hrachova V, Legrand J-C. Influence of C atom concentration
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.
[5] Kado S, Sekine Y, Nozaki T, Okazaki K. Diagnosis of atmospheric pressure low
temperature plasma and application to high efficient methane conversion. Catalysis
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 discharges. Catalysis Today 2003;
83: 101-109.
[7] Hwang B-B, Yeo Y-K, Na B-K. Conversion of CH 4 and CO2 to syngas and higher
hydrocarbons using dielectric barrier discharge. Korean J. Chem. Eng. Short
Communication 2003; 20 (4): 631-634.
[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. Chem. 2003; 9 (6): 787-
791.
[9] Kim S-S, Lee H, Na B-K, Song HK. Reaction pathways of the methane
decomposition in a dielectric-barrier discharge. Korean J. Chem. Eng. 2003; 20 (5):
869-872.
[10] Jeong H-K, Kim S-C, Han C, Hwaung L, Song HK, Na B-K. Conversion of methane
13
to higher hydrocarbons in pulsed DC barrier discharge at atmospheric pressure. Korean
J. Chem. Eng. 2001; 18 (2): 196-201.
[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: 1594-1601.
[12] Liu C, Marafee A, Mallinson R, Lobban L. Methane conversion to higher
hydrocarbons in a corona discharge over metal oxide catalysts with OH groups. Applied
Catalysis 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): 5803-5820.
[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. Chem. Eng. Japan 2001; 34 (11):
1356-1365.
[16] Fabry F, Flamant G, Fulcheri L. Carbon black processing by thermal Plasma.
Analysis of the particle formation mechanism. Chem. Eng Science 2001; 56: 2123-2132.
[17] Kim KS, Nam JS, Choi SI, Hong SH. Thermal plasma decomposition of methane for
production of hydrogen and carbon black. Proceedings of the 5 th International
Symposium on Pulsed Power and Plasma Applications 2004; 379-385.
[18] Yao S, Nakayama A, Suzuki E. Acetylene and hydrogen from pulsed plasma
conversion of methane. Catalysis Today 2001; 71: 219-223.
[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 barrier discharge, Plasma Chem.
Plasma Processing 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 discharge. Catalysis Today 2004; 89: 193-
200.
[21] Song HK, Choi J-W, Yue SH, Lee H, Na B-K. Synthesis gas production via
dielectric barrier discharge over Ni/γ-Al2O3 catalyst. Catalysis Today 2004; 89: 27-33.
[22] Hijikata K, Ogawa K, Miyakawa N. Methanol conversion from methane and water
vapor by electric discharge (effect of electric discharge process on methane
conversion). Heat Transfer-Asian Research 1999; 28 (5): 404-417.
[23] Dalaine V, Cormier JM, Lefaucheux P. A gliding discharge applied to H 2S
destruction. J. Appl. Phys. 1998; 83 (5): 2435-2441.
14
[24] Krawczyk K, Mlotek M. Combined plasma-catalytic processing of nitrous oxide.
Appl. Catal. B: Environ. 2001; 30: 233-245.
[25] Krawczyk K, Ulejczyk B. Decomposition of chloromethanes in gliding discharges.
Plasma Chem. Plasma Process. 2003; 23 (2): 262-281.
[26] Krawczyk K, Ulejczyk B. Influence of water vapor on CCl4 and CHCl3 conversion in
gliding discharge. Plasma Chem. Plasma Process. 2004; 24 (2): 155-167.
[27] Fridman A, Nester S, Kennedy LA, Saveliev A, Yardimci OM. Gliding arc gas
discharge. Prog. Energy Combust. Sci. 1999; 25: 211-231.
[28] Yardimci O-M, Saveliev AV, Fridman AA, Kendedy LA. Thermal and nonthermal
regimes of gliding arc discharge in air flow. J. Appl. Phys. 2000; 87 (4): 1632-1641.
[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): 4231-4237.
[30] Richard F, Cormier JM, Pellerin S, Chapelle J. Physical study of a gliding arc
discharge. J. Appl. Phys 1996; 79 (5): 2245-2250.
[31] Pellerien S, Richard F, Chapelle J, Cornier J-M, Musiol K. J. Phys. D: Appl. Phys.
2000; 33: 2407.
[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. 404-407.
[33] Song HK, Choi J-W, Lee H. Methane conversion in a gliding arc discharge. In: the
5th International Symposium on Pulsed Power and Plasma Applications. 2004. p. 375-
378.
[34] Savinov SY, Lee H, Song HK, Na B-K. The effect of vibrational of molecules of
plasmachemical reaction involving methane and nitrogen. Plasma Chem. Plasma
Process. 2003; 23 (1): 159-173.
15