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Corresponding author: Antonius Indarto; e-mail: indarto_antonius@yahoo.com
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Abstract
The direct conversion of methane using a dielectric barrier discharge has been
experimentally studied. Different values of flow rates and discharge voltages have been
used to investigate the effects on the conversion reaction products both qualitatively and
was 80% at an input flow rate of 5 mL/min and discharge voltage of 3.5 kV.
Experimental results show that the optimum condition was occurred at high discharge
voltage and higher input flow rate. In term of products distribution, higher flow rate or
hydrocarbon product was detected using thermal method, except hydrogen and C.
Increasing selectivity of ethane was found when Pt and Ru catalyst were existed in the
plasma reaction. Hydrogenation of acetylene in the catalyst surface can be the reason for
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1. Introduction
Methane, which is 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 availability 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
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 industrial 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 shipping by ocean-going
methane itself and carbon dioxide derived from methane combustion are greenhouse
gases.
Natural gas can be converted to fuels and chemicals in two ways, either via synthesis
processes for natural gas conversion involve 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
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The investigations of methane conversion to higher hydrocarbons in non-thermal
plasmas have been made worldwide by corona discharges, spark discharges, gliding arc,
Some researchers have tried to add auxiliary gases in the process, such as hydrogen [3],
air [3-5], oxygen [4-7], noble gas [5, 8]. Among them, mixing gas between methane and
CO2 was found to be the most promising technique to produce more valuable products,
such as synthesis gas [9-10]. Some others used the different types of plasma discharges
In the present research, 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 catalyst (Ni, Ru, Pt), supported by
Al2O3, has been prepared to investigate the effect of the products distributions.
2. Experimental Setup
Figure 1
Figure 1 shows a schematic diagram of the experimental setup in this study. Methane, as
source gas, was introduced into a cylindrical reactor at atmospheric pressure. Gases
were analyzed by gas chromatography. Details of each part of the system are described
A. Reactor
The reactor is a concentric cylinder with an inner metal electrode and an outer electrode
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of silver film coated around the tube. The plasma reactor consists of a pyrex tube (7.5
electrode. The effective gas volume and length of the reactor were 8.8 mL and 200 mm,
respectively. High voltage and frequency AC power supply were used in this
experiment. In order to maintain the similar configuration, e.g. gap distance, the reactor
capacitance was measured before experiment. The reactor capacitance was in the range
of 8.2-8.8 pF in air-gap environment. The same reactor size and configuration was used
The maximum voltage and frequency of the AC power supply (Auto electric, model
A1831) were 10 kV and 20 kHz. For measurement of voltage and current waveforms, a
P6015A), and a current probe (Fluke, model i400s) were used. The external input power
was measured by a digital power meter (Metex, model M-3860M) inserted at the ac
power input line. The amounts of actual supplied power were calculated by following
equation:
The waveform typical of voltage and current, used in this experiment, is shown in
Figure 2. For thermal process, a tubular furnace with temperature controller (Daepoong
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C. 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 calibrated mass flow controller
(Milipore, model FC-280SAV). Analysis of the gas sample was carried out using a gas
Column: Hayesep D 80/100) for measuring H2 and CH4, and a flame ionized detector
The evaluation of system performance was done based on products selectivity and
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
flow of converted CH 4
Energy efficiency = × 100% (4)
total power
A series of metal catalysts (Ni, Ru, Pt) was prepared by incipient wetness impregnation
method with Al2O3 as the support. The aqueous solutions of Ni, Ru, and Pt were made
England), and H2PtCl6.6H2O (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 O 2-rich
gas condition. Amounts of metal loaded were all settled to be 3 wt% of the catalyst. In
the plasma reaction experiment, 0.5 gram of catalyst was packed at the end of plasma
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zone to prevent the decomposition of products.
Figure 3
atmospheric pressure. In plasma experiments, the total flow rate was varied from 5
mL/min to 40 mL/min while 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 is produced at a higher voltage and a lower flow rate. The maximum
methane conversion reaches 80% at initial methane flow rate of 5 mL/min and voltage
of 3.5 kV. It shows that discharge voltage has a straight correlation with methane
conversion. The increase of the amplitude of voltage leads to the increase of plasma
density [12]. It can be seen also from the curve trend that at the conversion rate
decreases when the flow rate is increased. Lower flow rates will give longer chance for
the molecules to collide with energetic species, such as electron. At a higher flow rate,
the collisions are more effective although the percentage of conversion is lower, as seen
in Figure 4. More numbers of methane molecules are converted at higher flow rates than
that at lower ones. Instead of electron, energetic species from methane decomposition,
e.g. methyl radical (CH3.) and H., can initiate another effective collision with CH4. At
lower flow rates, the number of those species is less as the amount of methane flows to
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the reactor is also small. However, by increasing discharge voltage, the energy
efficiency is slightly increasing. Following the previous statement, the plasma reaction
is more effective to decompose methane at higher plasma density. This leads to the
conclusion that the optimum process is occurred at higher flow rate with higher
discharge voltage.
Figure 4 Figure 5
into smaller molecules, e.g. H2 and C, is more favorable that recombinant reaction to
produce higher hydrocarbons. At lower flow rate or longer residence time, higher
hydrocarbons that also produced during plasma reaction will be easily decomposed by
Electron that has a key factor to initiate the radical reaction in DBD process [13] can
Methyl radical (CH3.) will initiate the recombinant reaction of higher hydrocarbons and
hydrocarbons.
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CH3. + C2H3 C3H6 (10)
Because electron collision with molecules is faster than that with ion or radical [14], the
longer resident time of molecule in the plasma reaction will give a negative effect on
higher hydrocarbon formation or produce more stable H2 and C 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 of inner electrode. The research on coke formation has been
experimentally done by Le et al. [15] and simulated by Rhallabi and Chaterine [16].
Coke will be formed at the plasma area where the temperature is relatively high, e.g.
surface of the electrode. Close at the surface of the electrode, methane will be converted
CH4 C + 4 H (11)
CH4 C + 2 H2 (12)
This phenomenon was also occurred on our previous research of methane conversion
reaction by arc plasma [17] where the temperature is relatively higher than room
temperature.
Table 1
However, numerous amounts of H2 and C production were also found in the thermal
process. Table 1 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 it was found many in the output line of reactor. At flow rate of 20
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similar conversion of plasma experiment, it requires temperature more than 900oC. In
thermal process, supplied heat is the most driving factor in dissociating methane
CH4 C + 2 H2 (13)
The production of higher hydrocarbon was relatively small and un-detectable with our
All these reactions are highly endothermic, and high temperature operation is required
very short time reaction, less than 0.01 s, should be done [18] and it makes a difficulty
By comparing the experiment results, it shows that plasma process has an advantage on
higher hydrocarbon production. The existing of electrons and methyl radical, produced
during plasma process, could be the primary role on initiating the decomposition of
Table 2
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In order to improve the selectivity of products, 0.5 gram of three different catalysts has
been put in the end of plasma zone of the reactor. The purpose of this is to prevent the
produced higher hydrocarbon from the decomposition reactions. Table 2 shows the CH4
condition was done at methane flow rate of 20 mL/min. It shows that conversion of CH4
to other hydrocarbons was enhanced with the use of catalyst. Although the different
relatively small, the existence of catalyst was also help the cracking process of methane
molecules.
Interesting phenomena was found when Pt/γ-Al2O3 was used as the catalyst. Compared
the other hand, no acetylene (C2H2) was detected by our analysis instrument. According
to this result, the existence Pt catalyst in the plasma reaction will convert the produced
Low activation energy (~0 kJ/mol) of acetylene adsorption on Pt will make acetylene
The existing of numerous H, also attached on the surface, can initiate the series of
hydrogenation reactions:
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In our previous experiment, under non-catalytic reaction, the above reactions were
rarely occurred showed by small yields of C2H4 and C2H6 from C2H2 conversion [20].
The idea of this reaction mechanism, e.g. via intermediate C2H5, was supported by Dent
However, the similar phenomenon was also occurred when we put Ru/γ-Al2O3 catalyst.
Although the condition is less clear than Pt, by adding Ru catalyst, the selectivity of
catalyst, our observations did not find significant effect on products distribution of
methane conversion, in agreement with other experiment evidence that Ni is less active
4. Conclusions
The conversion of methane into hydrogen and higher hydrocarbons was experimentally
the residence time of molecule has influenced the reaction mechanism of the products.
Lower flow rate or longer residence time will make the reaction favors to be
hydrocarbons. By thermal process, the reaction will produce H2 and C. The existence of
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Acknowledgment
This research was supported by the National Research Laboratory program of the Korea
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Plasma AC power
Reactor supply
Bubble
catalyst flow meter
CH4
MFC
heater
GC
Thermal
Process
15
6000 200
150
4000
100
2000
Current (mA)
Voltage (kV)
50
0 0
- 50
- 2000
- 100
- 4000
voltage - 150
current
- 6000 - 200
- 25 - 15 -5 5 15 25
Time cycle (µs)
16
90
3 kV
80 3.2 kV
70 4 kV
60
Conversion (%)
50
40
30
20
10
0
0 10 20 30 40 50
Methane flow rate (mL/ min)
Figure 3. Effect of methane flow rates and discharge voltages on methane conversion
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0.16
0.14
Energy efficiency (mL/W)
0.12
0.1
0.08
0.06
0.04
3 kV
0.02 3.2 kV
4 kV
0
0 10 20 30 40 50
Methane flow rate (mL/ min)
Figure 4. Effect of methane flow rates and discharge voltages on process efficiency
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80
H2
70 C2
C3
60
C4
Selectivity (%)
50
40
30
20
10
0
0 10 20 30 40 50
Methane flow rate (mL/ min)
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Table 1. Methane conversion and products distribution comparison between plasma and thermal process
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Table 2. Effects of packed loading on methane conversion and products distribution
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