Journal of Natural Gas Chemistry 15(2006)–

Article

Methane Conversion Using Dielectric Barrier Discharge:

Comparison with Thermal Process and Catalyst Effects

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

Korea Institute of Science and Technology, Clean Technology Research Center,
P.O. Box 131, Cheongryang, Seoul 130-650, Korea
[ Manuscript received January 17, 2006; revised March 16, 2006 ]

Abstract: The direct conversion of methane using a dielectric barrier discharge has been experimentally
studied. Experiments with different values of flow rates and discharge voltages have been performed to
investigate the effects on the conversion reaction products both qualitatively and quantitatively. Experi-
mental results indicate that the maximum conversion of methane has been 80% at an input flow rate of 5
ml/min and a discharge voltage of 3.5 kV. Experimental results also show that the optimum condition has
occurred at a high discharge voltage and higher input flow rate. In terms of product distribution, a higher
flow rate or shorter residence time can increase the selectivity for higher hydrocarbons. No hydrocarbon
product was detected using the thermal method, except hydrogen and carbon. Increasing selectivity for
ethane was found when Pt and Ru catalysts presented in the plasma reaction. Hydrogenation of acetylene
in the catalyst surface could have been the reason for this phenomenon as the selectivity for acetylene in
the products was decreasing.
Key words: plasma; dielectric barrier discharge; thermal process; methane conversion; catalyst

1. Introduction shipping by ocean-going vessels is expensive. Approx-

Methane, which is a primary constituent of most
natural gas reserves, is currently being used for home
and industrial heating as well as for the generation
of electrical power. In many respects, methane is an
ideal fuel for these purposes because of its availabil-
ity in most populated centers, its ease of purification
to remove sulfur compounds, and the fact that among
the hydrocarbons it has the largest heat of combustion
relative to the amount of CO2 formed. On the other
hand, methane is a greatly underutilized resource for
chemicals and liquid fuels.
Moreover, the reserves are increasing more rapidly
than those of liquid petroleum. Much of the methane
is found in regions that are far removed from indus-
trial complexes and often it is produced off shore [1].
Pipelines may not be available for transporting this
remote gas to potential markets and liquefaction for
∗ Corresponding author. E-mail: indarto antonius@yahoo.com.
imately 11% of this gas is re-injected, and unfortu-
nately, another 4% is flared or vented [2], which is a
waste of a hydrocarbon resource. Both methane and
carbon dioxide derived from methane combustion are
greenhouse gases.
Natural gas can be converted to fuels and chem-
icals in two ways, either via synthesis gas or directly
into higher hydrocarbons or methanol. Today, most
commercial processes for natural gas conversion in-
volve synthesis gas as an intermediate. However,
extensive research is presently being carried out on
different possible routes for the direct conversion of
natural gas to improve the selectivity and yield of
higher hydrocarbons to meet the industrial and eco-
nomical demands.
The investigations of methane conversion to
higher hydrocarbons in non-thermal plasmas have
been made worldwide by corona discharges, spark dis-
2 Antonius Indarto et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006
charges, gliding arc or dielectric barrier discharges
(DBD) at atmospheric pressure and ambient temper-
ature. Some researchers have tried to add auxiliary
gases in the process, such as hydrogen [3], air [3–5],
oxygen [4–7] and noble gas [5,8]. Among them, mix-
ing gas between methane and CO2 was found to be
the most promising technique to produce more valu-
able products, such as synthesis gas [9,10]. Some
others used different types of plasma discharges that
could possibly produce different product distribution
[10,11].
In the present research, a comprehensive study
on the performance of plasma and thermal treatment
for methane conversion has been undertaken. Plasma
process was done on a dielectric barrier discharge
(DBD). A series of metal catalysts (Ni, Ru, Pt), sup-
ported by Al2 O3 , had been prepared to investigate
the effect of the products distributions.
2. Experimental setup
Figure 1 shows a schematic diagram of the exper-
imental setup. Methane, as the source gas, was in-
troduced into a cylindrical reactor under atmospheric
pressure. Gases were analyzed by gas chromatogra-
phy. Details of each part of the system have been
described in the next sections.
Figure 1. Experimental Setup
2.1. Reactor
The reactor was a cylindrical pyrex tube (ID of 7.5
mm) with two parallel-straight wires (0.2 mm diame-
ter, stainless steel) as the inner metal electrode and an
outer electrode of silver film coated around the tube.
The effective gas volume and length of the reactor
were 8.8 ml and 200 mm, respectively. A high voltage
and frequency alternating current (AC) power supply
was used in this experiment. In order to maintain
a similar configuration for every experiment, for ex-
ample, the gap distance, the reactor capacitance was
checked and measured before the experiments. The
reactor capacitance was in the range of 8.2–8.8 pF in
air-filled gap conditions. The same reactor size and
configuration were used for the thermal (non-plasma)
process.
2.2. Power supply and heater
The maximum voltage and frequency of the AC
power supply (Auto electric, model A1831) were
10 kV and 20 kHz. To measure voltage and
current waveforms, a digital oscilloscope (Agilent,
model 54641A), a voltage divider (Tektronix, model
P6015A), and a current probe (Fluke, model i400 s)
were used. The external input power was measured
by a digital power meter (Metex, model M-3860 M)
inserted at the AC power input line. The amount
of actual power supplied were calculated by following
equation:
Z
Actual power = (V (t) × I(t))dt × frequency
The typical waveform of voltage and current, used
in this experiment, is shown in Figure 2. For the ther-
mal process, a tubular furnace equipped with a tem-
perature controller (Daepoong Industry, Korea) was
used.
Figure 2. Typical waveform of voltage and current
2.3. Materials preparation
All experiments were carried out using pure
methane (CH4 ) with purity higher than 99.99%. Flow
rate of the source gas was controlled by a cali-
brated mass flow controller (Milipore, model FC-
280SAV). Analysis of the gas sample was carried out
 Journal of Natural Gas Chemistry Vol. 15 No. 2 2006 3

using gas chromatography (YoungLin, model M600D) higher hydrocarbons.

with a thermal conductivity detector (TCD, Column: The evaluation of system performance was done
Hayesep D 80/100) for measuring H2 and CH4 , and a based on product selectivity and methane conversion
flame ionized detector (FID) for measuring CH4 and which are formulated as:
moles of H2 produced
Selectivity for H2 = × 100% (1)
2 × moles of CH4 converted
x × moles of Cx Hy produced
Selectivity for Cx Hy = × 100% (2)
moles of CH4 converted
moles of CH4 converted
Conversion of CH4 = × 100% (3)
moles of initial CH4
moles of CH4 converted
Energy efficiency = × 100% (4)
total power
A series of metal catalysts (Ni, Ru, Pt) were pre- more effective although the percentage of conversion
pared by the incipient wetness impregnation method is lower, as seen in Figure 4.
with Al2 O3 as the support. The aqueous solutions of
Ni, Ru, and Pt were made by dissolving NiCl2 ·6H2 O
(Kanto Chemical Co, Japan), RuCl3 ·3H2 O (Enger-
hard, England), and H2 PtCl6 ·6H2 O (Next Chimica,
South Africa) precursors in aqua regia. All catalysts
were dried at 388 K for 2 h, followed by calcination
at 873 K for 3 h in O2 -rich gas condition. Reduction
of catalysts was done by flowing hydrogen at 673 K
for 2 h. The amounts of metals loaded were all set-
tled to be 3% of the catalyst. In the plasma reaction
experiment, 0.5 grams of the catalyst was packed at
the end of plasma zone to prevent the decomposition
of products. Figure 3. Ef fect of methane f low rates and dis-
charge voltages on methane conversion
3. Result and discussion (1) 3 kV (2) 3.2 kV, (3) 4 kV

3.1. Plasma and thermal process

Methane conversion under plasma and thermal

process was conducted under atmospheric pressure.
In plasma experiments, the total flow rate was varied
from 5 ml/min to 40 ml/min and the voltage was set
at 3, 3.2, and 3.5 kV. Figure 3 shows the effects of
input methane flow rate and voltage on the plasma
process. Higher conversion of methane is produced at
higher voltages and lower flow rates. The maximum
methane conversion reaches 80% at initial methane
flow rate of 5 ml/min and voltage of 3.5 kV. This
shows that discharge voltage has a straight correlation Figure 4. Ef fect of methane f low rates and dis-
with methane conversion. The increase of the ampli- charge voltages on process ef f iciency
tude of voltage leads to the increase of plasma den- (1) 3 kV (2) 3.2 kV, (3) 4 kV
sity [12]. It can also be seen from the curve trend that
the conversion rate decreases when the flow rate is in- More numbers of methane molecules are con-
creased. Lower flow rates will give a longer chance for verted at higher flow rates than at lower ones. Instead
the molecules to collide with energetic species, such of electrons, energetic species from methane decompo-
as electrons. At a higher flow rate, the collisions are sition, e.g. methyl radical (CH3 ·) and H·, can initiate
4 Antonius Indarto et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

another effective collision with CH4 . At lower flow reaction:

rates, the number of those species is less as the amount CH4 + e −→ CH4 · + e (5)
of methane that flows to the reactor is also small. CH4 · −→ CH3 · + H· (6)
However, by increasing discharge voltage, the energy
efficiency is slightly increased. Following the previ- Methyl radical (CH3 ·) will initiate the recombi-
ous statement, the plasma reaction is more effective nant reaction of higher hydrocarbons and hydrogen
to decompose methane at a higher plasma density. radical (H·) has a tendency to be a reducer or decom-
This leads to the conclusion that the optimum process poser reactant for higher hydrocarbons.
occurrs at higher flow rate with higher discharge volt-
CH3 · + CH3 · −→ C2 H6 (7)
ages.
CH3 · + CH3 · −→ C2 H4 + H2 (8)
Figure 5 shows the product distribution of
methane conversion by the plasma process. High se- Cx Hy + H· −→ Cx Hy−1 + H2 (9)
lectivity for H2 is produced at a low input flow rate. CH3 · + C2 H3 −→ C3 H6 (10)
Fragmentation of methane into smaller molecules, e.g.
Instate of H·, decomposition of higher hydrocar-
H2 and C, is more favorable that recombinant reac-
bon was also caused by electrons. Because electron
tion to produce higher hydrocarbons. At lower flow
collision with molecules is faster than that with ions or
rates or at longer residence time, higher hydrocarbons
radicals [14], the longer resident time of molecules in
that are also produced during the plasma reaction will
the plasma reaction will give a negative effect on the
be easily decomposed by electron and other energetic
formation of higher hydrocarbon and produce more
species.
H2 and C molecules than that in shorter resident time.
In case of coke (C solid), it was produced mostly at
the wall of the reactor and the surface wire of inner
electrode. The research on coke formation has been
experimentally done by Le et al. [15] and numeri-
cally simulated by Rhallabi and Chaterine [16]. Coke
will be formed at the plasma regions where the tem-
perature is relatively high, for example, at the sur-
face of the electrode. At the surface of the electrode,
methane will be converted into C and 4 H or H2 .
CH4 −→ C + 4H (11)
CH4 −→ C + 2H2 (12)

Figure 5. Ef fect of methane f low rates on products
distribution at discharge voltage of 3.5 kV
(1) C2 (2) H2 , (3) C3 (4) C4
Electron which has a key factor to initiate the
radical reaction in DBD process [13] can lead to the
This phenomenon also occurred in our previous
research of methane conversion reaction by arc plasma
[17] where the temperature was much higher than
room temperature.
However, numerous amounts of H2 and C produc-
tion were also found in the thermal process. Table 1

Table 1. Methane conversion and product distribution comparison between plasma and thermal processes
CH4 Selectivity (%)
conversion (%) H2 C2 H 2 C2 H 6 C3 H 6 C3 H 8 n-C4 H10 i-C4 H10
Plasma 54.97 35.29 4.85 20.89 2.01 12.42 5.90 4.64
51.11 29.22 7.36 23.19 3.36 13.33 6.11 7.37
25.01 34.77 5.06 25.48 1.73 13.89 4.42 4.95
22.37 38.46 9.30 42.75 2.98 19.79 5.85 7.67
Thermal 54.95 65.73
50.42 68.58
25.60 77.57
13.35 84.04
7.05 91.60
 Journal of Natural Gas Chemistry Vol. 15 No. 2 2006 5

shows the products comparison between plasma and
thermal process. Most of products of thermal process
were dominated by H2 and C. Solid carbon was not
measured, but much of it was found in the output
line of the reactor. At a flow rate of 20 ml/min, the
conversion of methane was begun at temperature of
700 ℃. To achieve similar conversion as in the plasma
experiment, it required the temperature to be more
than 900 ℃. In the thermal process, supplied heat is
the most driving factor in dissociating methane mole-
cules into H2 and C.
CH4 −→ C + 2H2 (13)
The production of higher hydrocarbon was rela-
tively small and un-detectable on using our analysis
instrument. Methane can be converted directly into
higher hydrocarbons, such as C2 hydrocarbons and
hydrogen via thermal coupling reactions:

2CH4 −→ C2 H2 + 3H2 , ∆H298 =3765 kJ/mol (14)

2CH4 −→ C2 H4 + 2H2 , ∆H298 =2023 kJ/mol (15)
2CH4 −→ C2 H6 + H2 , ∆H298 =651 kJ/mol (16)

All these reactions are highly endothermic, and
high temperature operation is required to obtain fa-
vorable thermodynamics. In order to avoid the de-
composition of products, very short time reaction,
less than 0.01 s, should be performed [18] and con-
sequently, this makes it difficult to achieve high con-
version of methane.
By comparing the experiment results, it can
be seen that the plasma process has an advantage
on higher hydrocarbons production. The existence
of electrons and methyl radicals, produced during
plasma process, could be the primary role in initiat-
ing the decomposition of methane and recombination
reactions of higher hydrocarbons.
3.2. Catalyst ef fect
In order to improve the selectivity of products,
0.5 grams of three different catalysts have been put
at the end of plasma zone of the reactor. The pur-
pose of this is to prevent the production of higher
hydrocarbons from decomposition reactions. Table 2
shows the CH4 conversion and product distribution
with different material packs. The experiment was
conducted at a methane flow rate of 20 ml/min. It
shows that the conversion of CH4 to other hydrocar-
bons was enhanced with the use of catalyst. Although
the difference was relatively small, the existence of
catalyst helped the cracking process of methane mole-

Table 2. Ef fects of dif ferent material packs loading on methane conversion and products distribution
CH4 Selectivity (%)
conversion (%) H2 C2 H 2 C2 H 6 C3 H 6 C3 H 8 n-C4 H10 i-C4 H10
Empty 43.42 34.52 5.13 25.73 0.00 11.73 5.25 4.81
γ-Al2 O3 42.50 39.69 7.62 26.31 2.69 15.85 5.74 5.56
Ni/γ-Al2 O3 48.06 38.89 5.23 27.97 2.31 14.02 4.92 5.31
Ru/γ-Al2 O3 48.13 33.55 2.65 30.22 0.00 13.47 5.08 5.36
Pt/γ-Al2 O3 47.00 32.92 0.00 34.87 0.00 16.36 5.51 6.00

cules. Interesting phenomena was found when Pt/γ- C2 H2(g) −→ C2 H2(surf) (17)
Al2 O3 was used as the catalyst. Compared to non-
catalyst treatment, the selectivity for ethane (C2 H6 ) The existance of numerous H atoms, also attached
was higher by a factor of 1.35. On the other hand, on the surface of catalyst, can initiate the series of hy-
no acetylene (C2 H2 ) was detected by our analysis in- drogenation reactions:
strument. According to this result, the existence of C2 H2(surf) + H(surf) −→ C2 H3(surf) (18)
Pt catalyst in the plasma reaction would convert the C2 H3(surf) + H(surf) −→ C2 H4(surf) (19)
produced acetylene into ethane by the hydrogenation C2 H4(surf) + H(surf) −→ C2 H5(surf) (20)
reaction on the surface of catalyst.
C2 H5(surf) + H(surf) −→ C2 H6(surf) (21)
Low activation energy (∼0 kJ/mol) of acetylene
adsorption on Pt will make acetylene attach easily to In our previous experiment, under the non-
the surface of the catalyst [19]. catalytic reaction, the above reactions rarely oc-
6 Antonius Indarto et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006
curred. This was shown by small yields of C2 H4 and
C2 H6 from C2 H2 conversion [20]. The idea of this
reaction mechanism, for example, via intermediate
C2 H5 , was supported by Dent et al’s investigation
[21].
However, a similar phenomenon also occurred
when Ru/γ-Al2 O3 catalyst was used. Although the
condition was less clear than Pt, by adding Ru cata-
lyst, the selectivity for ethane increased and followed
by a decreased selectivity for acetylene. In term of Ni
catalyst, no significant effects on product distribu-
tion of methane conversion were observed, which was
in agreement with other experiment evidence that Ni
is a less active catalyst for hydrogenation than Pt [19].
4. Conclusions
The conversion of methane into hydrogen and
higher hydrocarbons was experimentally investigated
in a dielectric barrier discharge and a thermal process.
In plasma process, the residence time of molecules
had influenced the reaction mechanism of the prod-
ucts. Lower flow rate or longer residence time would
make the reaction favor the dissociation of methane
into smaller molecules than recombinant reaction of
higher hydrocarbons. By thermal process, the reac-
tion will produce H2 and C. The existence of electrons
in plasma process gave an advantage on the higher hy-
drocarbon production.
In order to increase the selectivity of products, the
plasma-catalyst process has been performed. Pt and
also Ru catalyst show a significant effect on increasing
production of ethane by transforming the produced
acetylene by hydrogenation reactions.
Acknowledgements
This research was supported by the National Re-
search Laboratory program of the Korea Minister of
Science and Technology.
References
[1] Stern J, Royal Institute of International Affairs, Re-
port, July 2002
[2] Lercher J A, Bitter J H, Steghuis A G, Van Ommen
J G, Seshan K. Catalytic Science Series 1 (Environ-
mental Catalysis.), 1999, 103
[3] Liu C J, Mallinson R, Lobban L. J Catal, 1998,
179(1): 326
[4] Zhou L M, Xue B, Kogelschatz U, Eliasson B. Plasma
Chem Plasma Process, 1998, 18(3): 375
[5] Indarto A, Choi J W, Lee H, Song H K. Energy, in
press
[6] Cormier J M, Rusu I. J Phys D: Appl Phys, 2001,
34(18): 2798
[7] Nozaki T, Hattori A, Okazaki K. Catal Today, 2004,
98(4): 607
[8] Thanyachotpaiboon K, Chavadej S, Caldwell T A,
Lobban L L, Mallinson R G. AIChE J, 1998, 44(10):
2252
[9] Hwang B B, Yeo Y K, Na B K. Korean J Chem Eng,
2003, 20(4): 631
[10] Song H K, Lee H, Choi J W, Na B K. Plasma Chem
Plasma Process, 2004, 24(1): 57
[11] Lia X S, Zhu A M, Wang K J, Xu Y, Song Zh M.
Catal Today, 2004, 98(4): 617
[12] Choi Y H, Kim J H, Hwang Y S. Thin Solid Films,
2005, in press
[13] Eliasson B, Kogelschatz U. IEEE Trans Plasma Sci,
1991, 19(6): 1063
[14] Lieberman M A, Lichtenberg A J, Principles of
Plasma Discharges and Material Processing, 1st ed,
New York: John Wiley and Sons, 1994, 224
[15] Le H, Lobban L L, Mallinson R G. Catal Today, 2004,
89: 15
[16] Rhallabi A, Catherine Y. IEEE Trans Plasma Sci,
1991, 19(2): 270
[17] Indarto A, Choi J W, Lee H, Song H K. J Natur Gas
Chem, 2005, 14(1): 13
[18] Holmer A, Olsvik O, Rokstad O A. Fuel Process Tech,
1995, 42: 249
[19] Shustorovich E, Bell A T. Surface Sci, 1988, 205: 492
[20] Kim S S, Lee H, Na B K, Song H K. Korean J Chem
Eng, 2003, 20(5): 869
[21] Dent A L, Kokes R J. J Physic Chem, 1970, 20: 3653