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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-


imately 11% of this gas is re-injected, and unfortu-
Methane, which is a primary constituent of most nately, another 4% is flared or vented [a], which is a
natural gas reserves, is currently being used for home waste of a hydrocarbon resource. Both methane and
and industrial heating as well as for the generation carbon dioxide derived from methane combustion are
of electrical power. In many respects, methane is an greenhouse gases.
ideal fuel for these purposes because of its availabil- Natural gas can be converted t o fuels and chem-
ity in most populated centers, its ease of purification icals in two ways, either via synthesis gas or directly
t o remove sulfur compounds, and the fact that among into higher hydrocarbons or methanol. Today, most
the hydrocarbons it has the largest heat of combustion commercial processes for natural gas conversion in-
relative to the amount of COz formed. On the other volve synthesis gas as an intermediate. However,
hand, methane is a greatly underutilized resource for extensive research is presently being carried out on
chemicals and liquid fuels. different possible routes for the direct conversion of
Moreover, the reserves are increasing more rapidly natural gas t o improve the selectivity and yield of
than those of liquid petroleum. Much of the methane higher hydrocarbons t o meet the industrial and eco-
is found in regions that are far removed from indus- nomical demands.
trial complexes and often it is produced off shore [l]. The investigations of methane conversion to
Pipelines may not be available for transporting this higher hydrocarbons in non-thermal plasmas have
remote gas t o potential markets and liquefaction for been made worldwide by corona discharges, spark dis-
' Corresponding author. E-mail: hksong@kist.re.kr.
88 Antonius Indarto et al./ Journal of Natural Gas Chemistry Vol. 15 No. 2 2006

charges, gliding arc or dielectric barrier discharges was used in this experiment. In order to maintain
(DBD) at atmospheric pressure and ambient temper- a similar configuration for every experiment, for ex-
ature. Some researchers have tried to add auxiliary ample. the gap distance, the reactor capacitance was
gases in the process, such as hydrogen [3]. air [3-51. checked and measured before the experiments. The
oxygen [4-71 and noble gas j5.81. Among them. niix- reactor capacitance was in the range of 8.2-8.8 p F in
ing gas between methane and C 0 2 was found to be air-filled gap conditions. The same reactor size and
the most promising technique to produce more valu- configuration were used for the thermal (non-plasma)
able products, such as synthesis gas [9.10]. Some process.
others used different types of plasma discharges that
could possibly produce different product distribution 2.2. Power supply and heater
[lO,ll].
The maximum voltage and frequency of the AC
In the present research, a comprehensive study
power supply (Auto electric, model A1831) were
on the performance of plasma and thermal treatment
10 kV and 20 kHz. To measure voltage and
for methane conversion has been undertaken. Plasma
current waveforms, a digital oscilloscope (Agilent,
process was done on a dielectric barrier discharge
model 54641A), a voltage divider (Tektronix, model
(DBD). A series of metal catalysts (Ni. Ru. Pt). sup-
P6015A), and a current probe (Fluke, model i400 s)
ported by Al203. had been prepared to investigate
were used. The external input power was measured
the effect of the products distributions.
by a digital power meter (Metex, model M-3860 M)
inserted at the AC power input line. The amount
2. Experimental setup of actual power supplied were calculated by following
equation:
Figure 1 shows a schematic diagram of the exper-
imental setup. Methane, as the source gas. was in-
Actual power = / ( V ( t ) x I ( t ) ) d t x frequency
troduced into a cylindrical reactor under atmospheric
pressure. Gases were analyzed by gas chromatogra-
The typical waveform of voltage and current, used
phy. Details of each part of the system have been in this experiment, is shown in Figure 2. For the ther-
described in the next sections.
mal process, a tubular furnace equipped with a tem-
perature controller (Daepoong Industry, Korea) was
Plasma reactor used.
6000 , 200
4000
mad[ MFC
-
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 2.3. Materials preparation
mm) with two parallel-straight wires (0.2 mm diame-
ter, stainless steel) as an inner metal electrode and an All experiments were carried out using pure
outer electrode of silver film coated around t,he tube. methane (CH4) with purity higher than 99.99%. Flow
The effective gas volume and length of the reactor rate of the source gas was controlled by a cali-
were 8.8 ml and 200 mm, respectively. A high voltage brated mass flow controller (Milipore, model FC-
and frequency alternating current (AC) power supply 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 the most driving factor in dissociating methane mole-
thermal process. Most of products of thermal process cules into H2 and C.
were dominated by H2 and C. Solid carbon was not
measured, but much of it was found in the output CH4 f C+2H2 (13)
line of the reactor. At a flow rate of 20 ml/min, the The production of higher hydrocarbon was rela-
conversion of methane was begun at temperature of tively small and difficult t o detect on using our analy-
700 "C. To achieve similar conversion as in the plasma sis instrument. Methane can be converted directly
experiment, it required the temperature to be more into higher hydrocarbons, such as C2 hydrocarbons,
than 900 "C. In the thermal process, supplied heat is 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 3.2. Catalyst effect
high temperature operation is required to obtain fa-
vorable thermodynamics. In order to avoid the de- In order to improve the selectivity of products,
composition of products, very short time reaction, 0.5 grams of three different catalysts have been put
should be performed [lS] and consequently, this makes a t the end of plasma zone of the reactor. The pur-
a difficulty to achieve high conversion of methane. pose of this is t o prevent the production of higher
By comparing the experiment results, it can hydrocarbons from decomposition reactions. Table 2
be seen that the plasma process has an advantage shows the CH4 conversion and product distribution
on higher hydrocarbons production. The existence with different material packs. The experiment was
of electrons and methyl radicals, produced during conducted at a methane flow rate of 20 ml/min. It
plasma process, could be the primary role in initiat- shows that the conversion of CH4 to other hydrocar-
ing the decomposition of methane and recombination bons was enhanced with the use of catalyst. Although
reactions of higher hydrocarbons. 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

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