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Journal of Natural Gas Chemistry 15(2006)87-92

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.0. 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 and reaction products both qualitatively and quantitatively.
Experimental 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 4 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
t o remove sulfur compounds, and the fact that among
the hydrocarbons it has the largest heat of combustion
relative to the amount of COz 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 [l].
Pipelines may not be available for transporting this
remote gas t o potential markets and liquefaction for
' Corresponding author. E-mail: hksong@kist.re.kr.
imately 11% of this gas is re-injected, and unfortu-
nately, another 4% is flared or vented [a], 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 t o 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 t o improve the selectivity and yield of
higher hydrocarbons t o 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-
88 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 [3-51.
oxygen [4-71 and noble gas j5.81. Among them. niix-
ing gas between methane and C 0 2 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
[lO,ll].
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 Al203. 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.
Plasma reactor
mad[ MFC
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 p F 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:
Actual power = / ( V ( t ) x I ( t ) ) d t x 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.
6000 , 200
4000
-
100

s,
-
2
2000

0 O
z
E
Heater
u

>
3 E
0
-2000
Thermal process -100
-4000

Figure 1. Experimental Setup -200

-20 -10 0 10 20
Time cycle (ps)
2.1. Reactor Figure 2. Typical waveform of voItage and current

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 an inner metal electrode and an
outer electrode of silver film coated around t,he 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
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-
28OSAV). Analysis of the gas sample was carried out
 Journal of Natural Gas Chemistry Vol. 15 No. 2 2006 89

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 Ha = x 100%
2 x moles of CH4 converted
z x moles of C,H, produced
Selectivity for C,H, = x 100%
moles of CH4 converted
moles of CH4 converted
Conversion of CH4 = x 100%
moles of initial CH4
moles of CH4 converted
Energy efficiency = x 100%
total power
A series of metal catalysts (Ni, Ru, Pt) were pre- though the percentage of conversion is lower, as seen
pared by the incipient wetness impregnation method in Figure 4.
with A1203 as the support. The aqueous solutions of
Ni, Ru, and P t were made by dissolving NiClz.6H20
(Kanto Chemical Co, Japan), RuC13.3H20 (Enger-
hard, England), and H2PtC16.6H20 (Next Chimica,
South Africa) precursors in distilled water. All cata-
lysts were dried at 388 K for 2 h, followed by calcina-
tion at 873 K for 3 h in 02-rich gas condition. Reduc-
tion 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 0 1 ' " . 1 " ' ' " ' ' ~ " ' ' ' ' ' " '
0 10 20 30 40 50
the end of plasma zone to prevent the decomposition Methane flow rate (mlimin)
of products. Figure 3. Effect of methane flow 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. s
2
E 0.10 -
In plasma experiments, the total flow rate was varied v

c
from 5 ml/min to 40 ml/min and the voltage was set ;. 0.08 1
at 3, 3.2, and 4 kV. Figure 3 shows the effects of input E
methane flow rate and voltage on the plasma process. @ 0.06 -
0

Higher conversion of methane is produced at higher 5 0.04 ~

voltages and lower flow rates. The maximum methane

0.02 . . . . . . . . . . . . . . . . . . . . . . . , .
conversion reaches 80% at initial methane flow rate of
0 10 20 30 40 50
5 ml/min and voltage of 4 kV. 'This shows that dis- Methane f Low rate (mlimin)
charge voltage has a straight correlation with methane Figure 4. Effect of methane flow rates and dis-
conversion. The increase of the amplitude of voltage charge voltages on process efficiency
leads to the increase of plasma density [12]. It can (1) 3 kV ( 2 ) 3.2 kV, ( 3 ) 4 kV
also be seen from the curve trend that the conversion
rate decreases when the flow rate is increased. Lower More numbers of methane molecules are con-
flow rates will give a longer chance for the molecules verted at higher flow rates than at lower ones. Instead
to collide with energetic species, such as electrons. At of electrons, energetic species from methane decompo-
a higher flow rate, the collisions are more effective al- sition, e.g. methyl radical (CHS.) and H., can initiate
90 Antonius I n d a r t o et ai./ Journal of Natural Gas Chemistry VoI. 15 No. 2 2006

another effective collision with CH4. At lower flow

rates, the number of those species is less as the amount
of methane that flows to the reactor is also small.
reaction:
CH4 + e
H4C--
-
--i
H4C.-
CH3. + H. + e
(5)
(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- + CB3- -----t C2Hfj (7)
ages.
Figure 5 shows the product distribution of
CH3. + CH3. 4 C2H4 + H2 (8)
methane conversion by the plasma process. High se- C,H, +H. -+ C,H,-1. +Ha (9)
lectivity for H2 is produced at a low input flow rate. CH3. + C2H3. C3H6 (10)
Fragmentation of methane into smaller molecules, e.g. Instate of H., decomposition of higher hydrocar-
H2 and C, is more favorable than 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.
60 In case of coke (C solid), it was produced mostly at
"y the wall of the reactor and the surface wire of inner
50 eiectrode. The research on coke formation has been

- 40
5
experimentally done by Le et al. [15] and numeri-
cally simulated by Rhallabi and Chaterine [16]. Coke
.-
0
will be formed a t the plasma regions where the tem-
.?
c 30
-0

W
perature is relatively high, for example, at the sur-
v, 20 face of the electrode. At the surface of the electrode,
methane will be converted into C and 4 H or H2.
10

J CH4 + C+4H (11)

o ~ ' " ' ' " ' ' " " ' " ' ' " ' ' ~
0 10 20 30 40 50 CH4 -+ C+2Hz (12)
Methane flow rate (mlirnin)
Figure 5 . Effect of methane flow rates on products This phenomenon also occurred in our previous
distribution at discharge voltage of 4 k V research of methane conversion reaction by arc plasma
(1) Cz (2) Hz, 13) C3 (4) C4 [l?]where the temperature was much higher than
room temperature.
Electron which has a key factor to initiate the However, numerous amounts of Hz and C produc-
radical reaction in DBD process 1131 can lead to the 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 (%) J32 C2H2 CZH6 C3H6 C3H8 ?%-C4Hlo Z-CIHlO
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 91

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 "C. To achieve similar conversion as in the plasma
experiment, it required the temperature to be more
than 900 "C. In the thermal process, supplied heat is
the most driving factor in dissociating methane mole-
cules into H2 and C.
CH4 f C+2H2 (13)
The production of higher hydrocarbon was rela-
tively small and difficult t o detect on using our analy-
sis instrument. Methane can be converted directly
into higher hydrocarbons, such as C2 hydrocarbons,
and hydrogen via thermal coupling reactions:

2CH4 -----) C2H2 + 3H2, AH298=3765 kJ/mol

2CH4 + C2H4 + 2H2, AH298=2023 kJ/mol

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,
should be performed [lS] and consequently, this makes
a difficulty to achieve high conversion 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 effect
In order to improve the selectivity of products,
0.5 grams of three different catalysts have been put
a t the end of plasma zone of the reactor. The pur-
pose of this is t o 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

Table 2. Effects of different material packs loading on methane conversion and products distribution
~~

CH4 Selectivity (%)

conversion (%) H2 CzH2 C2H6 C3H6 C3H8 n-C4HlO i'C4H10
Empty 43.42 34.52 5.13 25.73 0.00 11.73 5.25 4.81
Y-A1203 42.50 39.69 7.62 26.31 2.69 15.85 5.74 5.56
Ni/~-A1203 48.06 38.89 5.23 27.97 2.31 14.02 4.92 5.31
Ru/y-AlnOs 48.13 33.55 2.65 30.22 0.00 13.47 5.08 5.36
Pt/~-Al203 47.00 32.92 0.00 34.87 0.00 16.36 5.51 6.00

catalyst helped the cracking process of methane mole-

cules. Interesting phenomena was found when Pt/y-
A1203 was used as the catalyst. The selectivity for
C2H2(g) - CaHa(surf)
The existance of numerous H atoms, also attached
(17)

ethane (C2H6) over Ptly-Al203 catalyst was 1.35 on the surface of catalyst, can initiate the series of hy-
times as high as that over non-catalyst treatment. On drogenation reactions:
the other hand, no acetylene (C2H2) was detected by C2H2(surf) + H(su,f) C2H3(surf) (18)
our analysis instrument. According to this result, the GH~(surf)+ H(surf) CaHli(surf) (19)
existence of Pt catalyst in the plasma reaction would
convert the produced acetylene into ethane by the hy-
Ca&(surf) + H(surf) + C2H5(surf) (20)
drogenation reaction on the surface of catalyst. C2HB(surf) + H(surf) ----f CZHG(surf) (21)
Low activation energy (-0 kJ/mol) of acetylene In our previous experiment, under the non-
adsorption on Pt will make acetylene attach easily to catalytic reaction, the above reactions rarely oc-
the surface of the catalyst 1191. curred. This was shown by small yields of C2H4 and
92 Antonius Indarto et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006
C~HG from C2H2 conversion [20]. The idea of this
reaction mechanism, for example, via intermediate
C2H.5, was supported by Dent et al’s investigation
[all.
However, a similar phenomenon also occurred
when Ruly-AlzOs catalyst was used. Although the
condition was less clear than P t , 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 P t
1191.
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. P t 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. The authors are thankful
to the Korea Institute of Science and Technology for
supports.
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