This article was published in an Elsevier journal.

The attached copy

is furnished to the author for non-commercial research and
education use, including for instruction at the author’s institution,
sharing with colleagues and providing to institution administration.
Other uses, including reproduction and distribution, or selling or
licensing copies, or posting to personal, institutional or third party
websites are prohibited.
In most cases authors are permitted to post their version of the
article (e.g. in Word or Tex form) to their personal website or
institutional repository. Authors requiring further information
regarding Elsevier’s archiving and manuscript policies are
encouraged to visit:

http://www.elsevier.com/copyright
 Author's personal copy

F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 2 14 –2 1 9

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Kinetic modeling of plasma methane conversion in a dielectric

barrier discharge

Antonius Indarto a,b,⁎, Nowarat Coowanitwong b , Jae-Wook Choi a ,

Hwaung Lee a , Hyung Keun Song a
a
Clean Technology Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul, Republic of Korea
b
School Environmental Resources Development, Asian Institute of Technology, P.O. Box 4, Klong Luang, Pathumthani, Thailand

AR TIC LE I N FO ABS TR ACT

Article history: Methane conversion by plasma offers a promising route to produce higher value-added
Received 7 February 2007 products. As plasma reaction is a relatively complex process, kinetic modeling is necessary
Received in revised form to obtain a general pattern of the complex interaction on the basis of chemical reaction and
13 September 2007 products. In this paper, we present a method to obtain the kinetic rate coefficient (k) from
Accepted 17 September 2007 the experimental data. Although plasma reaction was classified as chemically complex
interaction, the reactions showed a certain pattern of the mechanism. In pure methane
Keywords: injection, the decomposition of methane by plasma could initiate coupling reactions and
Plasma produce C2H6, C3H8, and C4H10. Dehydrogenation of C2H6 into C2H4 and then to C2H2 could be
Dielectric barrier discharge clearly seen by the higher value of the reaction rate constant of C2Hn + 2 to C2Hn − 2. Using the
Methane rate constant values (k) obtained by this method, the pathways of the methane conversion
Kinetic reaction by a dielectric barrier discharge can be drawn.
© 2007 Elsevier B.V. All rights reserved.

1. Introduction which is subsequently hydrogenated, e.g., to methanol [2]. In

The use of natural gas as a feedstock in the chemical and
pharmaceutical industry is an alternative to crude oil whose
supplies might run out in the next century. Methane (CH4), the
major component of natural gas, is widely distributed at sites
around the world and have a potential to be used as the
precursor to produce higher value-added products, for exam-
ple acetylene and ethylene.
There are mainly three approaches to converting CH4 into
higher hydrocarbons in a high temperature process: the direct
oxidative methane conversion (OMC), the Fischer–Tropsch pro-
cess via syngas, and the non-oxidative methane conversion [1].
Over the last decades, many researches have mainly
focused on oxygen-containing processes, either indirect ones
as in the Fischer–Tropsch process or direct ones as in the
oxidative methane conversion. In the Fischer–Tropsch pro-
cesses, CH4 is converted into hydrocarbons, via synthesis gas,
the presence of oxygen, the direct CH4 conversion to C2H6,
C2H4 (one of the most important raw materials in industrial
production cycles), C3Hn, C4Hn is thermodynamically feasible
(exothermic), whereas the oxygen-free or dehydrogenative
conversion is endothermic (two-step polymerization). OMC
has been investigated extensively [3,4] and is still most
frequently used due to its higher methane conversion
although suffering from low selectivity of C2+ [5].
The oxygen-free methane conversion, however, has only
been studied by a few groups [6–9]. The state of the art for this
process was recently summarized by Guczi et al. [10]. A major
disadvantage of the OMC is its low selectivity towards C2+,
because considerable amounts of CH4 are consumed forming CO
and CO2. In contrast to OMC, the non-oxidative methane
conversion (NOMC) by thermal process gives numerous
amounts of solid carbon and hydrogen [11] with less C2+
production. Higher hydrocarbon production via methyl coupling

⁎ Corresponding author. Clean Technology Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul
130-650, Republic of Korea. Tel.: +82 10 2296 3748.
E-mail address: indarto_antonius@yahoo.com (A. Indarto).

0378-3820/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.09.006
 Author's personal copy
F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 2 1 4–2 1 9
reactions occurred only with very short time and high tem-
perature reaction [12].
Non-oxidative plasma methane conversion (NOPMC) offers
a high selectivity towards C2+ products [11,13]. The reason for
focusing on oxygen-free methane conversion is therefore to
maintain the high C2+ selectivity, while simultaneously
enhancing the CH4 conversion and the C2+ yield, respectively.
The optimization of the NOPMC necessitates a detailed
knowledge of the gas-phase reactions that occur and their
kinetics.
In this present work, we develop a kinetic model for plasma
methane conversion to higher hydrocarbons. By finding the
kinetic rate constant (k), the global pathway of the reactions could
be drawn easily. The model includes the gas-phase transforma-
tion of molecules that exist in the reactant and the products.
Based on the comparison between experimental and simulation
data, it was found that the proposed kinetics well-accounted for
the reaction products of C2H2, C2H4, C2H6, C3H6, C3H8, i-C4H10, and
n-C4H10. The constructed model was applicable for the plasma
reaction using dielectric barrier discharge at atmospheric pres-
sure (c.a. 1 atm) and ambient temperature (c.a. 25 °C). The
presented kinetic model is a part of efforts encompassing the
oxygen-free plasma chemistry for methane conversion.
2. Experimental setup and algorithm
The schematic diagram of the experimental setup is shown in
Fig. 1. Details of each part of the system are described in the
following sections.
2.1. Plasma reactor and power system
The reactor used in the experiments is a cylindrical pyrex tube
(ID of 7.5 mm) with 2 parallel-straight wires (0.2 mm diameter,
stainless steel) as the inner metal electrode and silver film
coated at the outer side of tube as the outer electrode. The
effective volume and length of the reactor were 8.8 ml and
200 mm, respectively. A high frequency alternating current
(AC) power supply with a maximum voltage of 20 kV was
connected to the electrodes. The supplied power to the reactor
was maintained constant at 60 W, measured by a watt meter
(Metex model M-3860M).
Fig. 1 – Schematic diagram of experimental setup.
215
In order to maintain the similarity of the reactor configu-
ration, e.g. electrodes gap distance, the reactor capacitance
was checked by an RCL meter (Fluke model PM6304) before
and after experiments. The reactor capacitance was in the
range of 9.0–10.0 pF at ambient air condition.
2.2. Input gas and measurement system
All experiments were carried out by introducing eight different
hydrocarbons: CH4, C2H2, C2H4, C2H6, C3H6, C3H8, i-C4H10, n-C4H10.
CH4 has purity of 99.97% while other gases have purity of above
99.9%. A Gas Chromatography (YoungLin M600D, column: 30 ft of
Hayesep D) has been used to quantitatively analyze the amount
of products by flame ionization detection (FID) and thermal
conductivity detector (TCD). The FID system was capable to
detect compounds in hundreds of ppm level. Considering the
volume expansion and the compression of products, the output
line was connected to a bubble flow meter to measure the flow
difference of the products before and after reaction.
The products concentration and reactants conversion were
formulated as:
moles of Cx Hy converted
Conversion of Cx Hy ¼  100 ð1Þ
moles of initial Cx Hy
moles of Cm Hn produced
Concentration of Cm Hn ¼  100 ð2aÞ
total moles products
m  moles of Cm Hn produced
Selectivity of Cm Hn ¼  100 :
moles of Cx Hy converted
ð2bÞ
2.3. Model algorithm
In the kinetic model, the possibility of molecular transforma-
tion to any possible compounds that exist in the products or
the reactants was calculated. The reaction rate (dC / dt) of
single hydrocarbon was measured experimentally by injecting
pure compound to the reactor. Then, the product distribution
was calculated and the rate of molecular transformation
converted to other molecules could be obtained. From the
experimental analysis, eight hydrocarbons existed in the
products and those were (1) CH4, (2) C2H2, (3) C2H4, (4) C2H6,
(5) C3H6, (6) C3H8, (7) i-C4H10, and (8) n-C4H10. As we assume
 Author's personal copy

216 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 2 14 –2 1 9

that the reaction will occur in a 1st order reaction, the calcu- were introduced separately to the plasma reactor at
lation of each compound is as follows: atmospheric pressure (∼ 1 atm) and room temperature
(∼ 25 °C). The flow rate and supplied power were maintained
dCi Xn Xn
¼ kij Ci þ kji Cj ð3Þ similar at 30 ml/min and 60 W, respectively. These values
dt j¼1 j¼1 were obtained from the optimization of the previous
research [14] in order to avoid large amount of unknown
where n is the maximum value of i and j for k-set which is products and carbon deposition which were difficult to
8 and kij denotes the reaction rate constant of i molecule that measure.
converts into a specific j molecule. The assumption was Fragmentation reactions of methane into smaller mole-
chosen to simplify the calculation and make the data cules were more favorable than synthesis reactions of higher
comparable to each other. The value of kij will be 0 if i = j. hydrocarbons at lower input flow rates and higher supplied
2 3 power [11,15,16]. As higher hydrocarbons are more useful and
dC1 2 32 3 2 32 3
6 dt 7 k11 : : : k18 C1 : : : C8 k11 : : : k81 C1 : : : C1 valuable products, increasing flow rates and lowering supplied
6 7
6v
4 dC 5
7 ¼ 4 v ⋱ v 54 v ⋱ v 5 þ 4v ⋱ v 54 v ⋱ v 5
8 k81 : : : k88 C1 : : : C8 k18 : : : k88 C8 : : : C8 power can be the way to avoid above problems.
dt Table 1 shows the conversion rate of input gas and the
ð4Þ distribution of products after treated by dielectric barrier
discharge at flow rate of 30 ml/min and supplied power of
By solving Eq. (4), the calculation will result a set of kinetic 60 W. Except for the experiments initiated by C2H2 (run 2) and
rate constant (k) which can be arranged as: C3H6 (run 5), the total C and H atom balance between the
2 3 reactants and products of all plasma process approximately
0 k12 : : : k18
6 k21 0 ::: k28 7 closed to 100% which means that the molecular transforma-
k¼6 7: ð5Þ
4v v ⋱ v 5 tion of reactants to the products were almost perfectly
k81 : : : k87 0 identified. Small amounts of carbon deposition on the wall
and inner electrode were found but, as the values were
The value of k was obtained by an error minimization relatively small, those could be neglected in the calculation.
between model data and experimental data. In this particular It was a good achievement, since to obtain correct calculation
case, the minimization calculation was done employing of the kinetics, the C and H balance between reactants and
Matlab sub-routine module ‘fminsearch’ after simultaneous products should be equal. In the case when C2H2 and C3H6
integration of Eq. (4) using ‘ode23s’. The uniqueness of the were used as the reactant, the reaction produced a lot of solid
result was measured by calculating the mean-squared error of carbon and/or soot. We could not confirm whether the solid
each set value of kij obtained from eight different input gases product was coming from the polymerization of C2H2 and C3H6
which is expressed as: or agglomeration of monomolecular carbon. However, C2H2
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi and C3H6 are well-known as soot precursor in the pyrolysis or
uPP 2
u combustion process [17]. In this case, the similar phenomenon
t k  ki
s¼ ð6Þ has likely occurred in the plasma process.
n1
From Table 1, it can be figured out that when methane was
P
where n is the maximum size of k-set which is eight, k is the the reactant, the products were dominated by ethane (C2H6),
mean value of k-set. with selectivity of 37.5%, propane (C3H8), 25.6%, and butane
(normal- and iso-C4H10), 25.4%. This product composition has
a similarity with the result of Thanyachotpaiboon et al. [18],
3. Results and discussion who used DBD system and AC power supply similar to ours,
with slightly higher selectivity of propane and butane. The
In order to obtain the rate constant k in Eq. (5), eight hydrocarbon higher value of the selectivity was due to the use of a different
gases: CH4, C2H2, C2H4, C2H6, C3H6, C3H8, i-C4H10, and n-C4H10 method in the selectivity calculation. Thanyachotpaiboon

Table 1 – The reactant conversion and products distribution of plasma process

Reaction Conversion Products concentration [%] Atom balance
[%]
CH4 C2H2 C2H4 C2H6 C3H6 C3H8 i-C4H10 n-C4H10 Cout/Cin Hout/Hin [1]

CH4 13.8 86.20 0.17 0.45 2.04 0.00 0.93 0.26 0.43 0.95 1.01
C 2H 2 12.0 3.03 81.95 1.45 0.00 0.14 0.00 0.00 0.28 0.87 1.13
C 2H 4 15.7 2.67 3.31 84.30 0.68 0.38 0.67 0.67 1.84 0.95 0.98
C 2H 6 9.4 0.96 1.27 2.10 90.57 0.16 0.89 0.05 0.85 0.97 0.98
C 3H 6 9.8 0.70 1.60 2.48 0.46 80.16 2.23 0.99 0.57 0.89 1.01
C 3H 8 11.7 2.31 0.47 2.03 0.95 2.54 88.27 0.09 0.00 0.97 0.96
i-C4H10 16.7 2.36 2.35 4.02 1.65 3.19 1.39 83.33 5.94 1.04 1.00
n-C4H10 8.4 1.27 1.08 2.29 1.28 1.36 1.46 2.33 91.63 1.03 0.98
of Cm Hn produced
Note: [1]The calculation of H balance includes the H2 in the output and the selectivity of component follows: selectivity of Cm Hn ¼ n4  moles
moles of CH4 converted .
All data were obtained at a flow rate of 30 ml/min and a supplied power of 60 W.
 Author's personal copy
F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 2 1 4–2 1 9
et al. was using fractional method instead of carbon balance-
based calculation that we used.
Higher ethane selectivity could be obtained by coupling
reaction of methyl radical which also suggested by Zhao et al.
[19]. Abundant amounts of methyl radical could combine with
C2 molecules to form C3 hydrocarbons or with C3 molecules to
form C4 hydrocarbons [20].
In the case of other products, e.g. acetylene and ethylene,
those compounds could be produced due to stepwise dehydro-
genation reaction of ethane. The tendency of acetylene
formation from ethylene and ethylene from ethane by dehy-
drogenation reactions was clearly seen from run-4 of Table 1.
When ethane was the reactant, the selectivity for ethylene was
29% which is two times higher compared when acetylene was
used as the reactant. A similar phenomenon also occurred in the
case of acetylene formation. The selectivity of acetylene
production reached 27.7% when ethylene was the reactant
and only the selectivity was 3.2% when methane was the
reactant. An interesting phenomenon occurred when acetylene
was used as the reactant which could be an important part to
describe the kinetic pathways. Acetylene was converted mostly
into methane, 40%, and at the same time, it also produced
ethylene (39%), and n-butane (15%). Those products required
hydrogen to react with acetylene.
C2 H2 þ 3H2 →2CH4
C2 H2 þ H2 →C2 H4
2C2 H2 þ 3H2 →iC4 H10
2C2 H2 þ 3H2 →nC4 H10 :
In order to supply H2, fragmentation of C2H2 as the
intermediate reaction was needed.
C2 H2 →2C þ H2 :
As the total C atom of gaseous products was only 87%
compared to the total C atom of reactant, reaction 11 high
possibly occurred in plasma zone and responsible for the
formation of molecular solid carbon formation. The proposed
reaction 11 was also supported by hydrogen atom ratio of the
products to the reactant which closed to 1 that means there
was no loss of hydrogen atom in the process.
Coupling reactions between two C2 compounds could form
butane and the long-chain type (n-C4H10) was more favorable
than the iso-type (i-C4H10). It was simply because the adduct
reaction of two C2 moieties occurred without any molecular
steric hindrance although later on, it converted to iso-form as
iso-form is thermodynamically more stable than normal-type.
C2 H4 þ C2 Hx þ ð8−xÞ=2 H2 →nC4 H10 :
In the case of C3H6 consumption process, the reactions
occurred by two main parallel ways:
C3 H6 þ H2 →C3 H8
C3 H6 →C2 H4 þ C þ H2 :
217
From these two reactions, we would obtain less amount of
total C atom number in the gaseous products due to carbon solid
formation in Eq. (14). It was confirmed by experimental result
that the total C atom in the gaseous products was only 89%
compared to the original reactant. Instead of above conversion
reactions, C3H6 could be formed by dehydrogenation of C3H8
(reverse reaction of Eq. (13)) or fragmentation of i-C4H10. This
idea was supported by results of pure C3H8 and i-C4H10 injection.
When C3H8 and i-C4H10 were the reactant, the selectivity of C3H6
reached 44% and 17%, respectively. The proposed reactions
mechanism follows:
C3 H8 →C3 H6 þ H2 ð15Þ
iC4 H10 →C3 H6 þ CH4 ð16Þ
iC4 H10 →C3 H6 þ CH2 þ H2 : ð17Þ
C3H6 produced from Eq. (16) could be suffered from reverse
reaction of n-C4H10 formation
C3 H6 þ CH4 →nC4 H10 : ð18Þ
In this case, the probability of Eq. (17) is higher than Eq. (16)
as high concentration of H2 was found in the product stream.
Moreover, coupling reaction of :H2 diradical could form C2H4,
as its selectivity reaches 14%, follows [21]:
ð7Þ
CH2 þ CH2 →C2 H4 : ð19Þ
ð8Þ
Taken from all above explanation, the reaction pathways of
methane conversion in a dielectric barrier discharge at flow rate
ð9Þ
of 30 ml/min and supplied power of 60 W are shown in Fig. 2.
ð10Þ
4. Kinetic model
In order to quantify the rate of the reaction, a kinetic model
ð11Þ was built according to the algorithm (Section 2.3). Some
assumptions were used to reduce the complexity of the
reactions: (i) all the reactions were first order; (ii) the formation
of coke and hydrogen was negligible in the model. All
calculations were performed using Matlab by exploiting
‘ode23s’ to solve a set of differential equations in Eq. (4). The
reaction rate constants, k (shown in Eq. (5)) were obtained by
least-square calculation of the calculated values and the
experimental results using ‘fminsearch’ module. The estimat-
ed reaction rate constants (k) are listed in Table 2. Higher k
value means the reactant transformation to certain product is
easier.
From Table 2, the value of the k-set supports our previous
statements that the decomposition of methane will produce
C2H6 (k14), C3H8 (k16), and C4 (k17 and k18). Low value of k13
ð12Þ
ð13Þ
ð14Þ Fig. 2 – The pathway reaction of methane conversion.
 Author's personal copy

218 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 2 14 –2 1 9

Table 2 – reaction rate coefficient (k)

kij (1) CH4 (2) C2H2 (3) C2H4 (4) C2H6 (5) C3H6 (6) C3H8 (7) i-C4H10 (8) n-C4H10

(1) CH4 0 (0.0) 0.06 (5.3) 0.18 (11.6) 0.5 (6.5) 0.02 (7.5) 0.3 (9.8) 0.13 (10.7) 0.29 (11.1)
(2) C2H2 1.31 (8.1) 0 (0.0) 0.17 (12.0) 0.18 (8.4) 0.31 (38.6) 0.06 (20.7) 0.14 (16.1) 1.47 (9.1)
(3)C2H4 0.08 (8.5) 1.79 (8.6) 0 (0.0) 0.01 (18.9) 0.22 (6.2) 0.02 (15.6) 0.25 (9.1) 1.01 (9.9)
(4) C2H6 0.11 (17.3) 0.3 (6.1) 1.03 (9.2) 0 (0.0) 0.07 (18.0) 0.67 (21.7) 0.15 (4.7) 0.94 (13.7)
(5) C3H6 0.09 (21.8) 0.23 (35.1) 0.33 (7.8) 0.14 (7.0) 0 (0.0) 0.53 (10.9) 0.54 (8.5) 0.53 (7.1)
(6) C3H8 0.06 (13.5) 0.97 (11.3) 0.16 (28.2) 0.49 (8.1) 0.48 (10.8) 0 (0.0) 0.7 (7.9) 0.97 (13.3)
(7) i-C4H10 0.06 (20.6) 0.67 (36.2) 1.28 (7.7) 0.89 (21.7) 1.28 (8.2) 1.45 (8.3) 0 (0.0) 2.45 (8.9)
(8) n-C4H10 0.74 (7.2) 1.07 (21.8) 2.27 (6.4) 0.39 (8.0) 1.05 (18.3) 0.33 (23.8) 1.38 (7.7) 0 (0.0)
−1
Note: The value of kij refers to the value of reaction rate coefficient of molecule i to molecule j. All k values are in mol min ; the standard
deviation values inside the parentheses are in % unit.

(CH4 → C2H4) and k12 (CH4 → C2H2) shows that acetylene and conversion rate of i-butane is 10% lower than that of n-butane,
ethylene were not coming from the direct methane conver- which means that i-butane is more stable than n-butane.
sion. Losing two H's and coupling with another triplet :CH2 to The reverse reaction to produce methane was mostly
form ethylene or losing three H's and coupling with duplet ·CH coming from acetylene, confirmed by k21 (1.31 min− 1) which
required many steps. There was also a possibility of attack by is higher than for other reactants. From this data, we are also
other species before completing the radical coupling reaction. able to determine that the decomposition of higher hydro-
Acetylene and ethylene were formed by stepwise dehydro- carbons will not produce CH4 as the product but instead will
genations of ethane. The dehydrogenation reactions of C2H6, produce ·CH3, :CH2, or ·CH. The existence of C1 radical
occurred in the plasma reaction, could be detected by k43 hydrocarbons could help to increase the selectivity of C2, C3,
(C2H6 → C2H4), 1.03 min− 1, then k32 (C2H4 → C2H2), 1.79 min− 1. and C4 compounds by coupling reactions. Unfortunately, as
The trend of the result was similar to that of Jeong et al. [22] this method is just counting the tendency of the reaction
which was also suggested by Kozlov et al. [23] that pathways of pathway, the presence of intermediate species could not be
C2 dehydrogenation reactions will follow: confirmed scientifically.
By taking only the important and significant k values, we
CH4 YC2 H6 Y C2 H4 YC2 H2 : can draw a global reaction pattern diagram of methane
conversion (presented in Fig. 2). It shows that C2H4 has an
The above stepwise dehydrogenation reaction was also
important role as a branching agent to diversify the reaction
identified in the thermal coupling of methane [24].
mechanism. This idea is supported by the data because C2H4
Interestingly, n-butane hydrocarbon could be formed
was easier to produce than other C2 compounds from the
from any hydrocarbons species, confirmed by higher value
cracking of higher hydrocarbons (C3 and C4). To form C2H6, the
of kx8, N0.5 min− 1, except for methane. This result could
reactions should be terminated by recombination reaction
answer the high yield production of C4 compounds that
with H2. On the other hand, C2H2 formation required further
usually produced in DBD using AC power supply. This result
dehydrogenation reaction to remove two hydrogen atoms.
confirmed the previous research that the addition of higher
Instead of dehydration reaction into C2H2, coupling reaction of
hydrocarbons, e.g. ethane, on plasma methane conversion
C2H4 could form n-C4H10 (Eq.(12)) or react with CH2 radical to
would increase the selectivity of butane [18]. Later on,
form C3H6.
intermolecular transformation of n-butane to i-butane
occurred as i-butane is thermodynamically more stable
than n-butane, showed by k87 (1.38 min− 1). In a parallel
way, homolytic dissociation of n-butane to C2 hydrocarbons
(acetylene and ethylene) is confirmed by k82 (1.07 min− 1) and
k83 (2.27 min− 1) or into propene by k85 (1.05 min− 1). Usually,
decomposition of higher hydrocarbon to lower hydrocarbons
results higher reaction rate constant k (around 0.5–2 min− 1)
compared to the formation of higher hydrocarbons from the
lower ones. It was acceptable since the dissociation reaction,
e.g. decomposition of one butane molecule, will produce
double C2 molecules or even more if it decomposed to C1
molecules.
Instead of coming from the intermolecular transforma-
tion of n-butane, the formation of i-butane could be formed
from C3 compounds, k58 = 0.54 min− 1 and k68 = 0.7 min− 1.
Although i-butane will be consumed in further reaction mostly Fig. 3 – The comparison between experimental and model
to n-butane, by k78 = 2.54 min− 1, we have to consider the simulation results of binary mixture methane + acetylene at
conversion comparison between n-butane and i-butane. The the flow rate of 30 ml/min and supplied power of 60 W.
 Author's personal copy
F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 2 1 4–2 1 9
In order to check the correctness of the model, a binary
mixture of methane and acetylene was injected to the reactor
at the total flow rate of 30 ml/min and supplied power of 60 W.
As shown in Fig. 3, the model calculation was found to be in
good agreement with the experimental data. It also means
that the proposed values of reaction rate constant, k, as well as
the model can rationalize the plasma mechanism of methane
and/or hydrocarbon conversion.
5. Conclusions
The kinetics of methane conversion in a dielectric barrier
discharge at a supplied power of 60 W was studied. It shows
that C2H4 has an important role on the global mechanism,
having a function as a branching molecule which is able to
diverse the global reaction mechanism. Similar to thermal
methane decomposition reaction, dehydrogenation of C2H6
has also occurred and producing C2H4 then continued by
formation of C2H2. Coupling reaction of C2H4 with other C2
hydrocarbons would yield butane which usually has a long-
chain molecule (normal-form). Using this method which is
relatively simple, the pathway pattern of CH4 conversion
could be obtained. It will be a good advantage to predict or
optimize the end products of direct methane conversion by a
dielectric barrier discharge. Further model improvement is
still necessary to be able to conduct the calculation in various
conditions, e.g. different flow rates, which are not covered in
this research.
Acknowledgments
The authors would like to thank the Korea Institute of Science
and Technology (KIST) and the Korea University (KU) for the
study supports. The first author would like to express his
appreciation to the Università degli studi di Torino for the
support during the study period in Turin, Italy.
REFERENCES
[1] M.J. Gradassi, N.W. Green, Economics of natural gas conversion
processes, Fuel Process. Technol. 42 (1995) 65–83.
[2] A.T. Bell, Mechanisms of Fischer–Tropsch Synthesis, 1984,
NTiS report number: DE84014608.
[3] H. Zanthoff, M. Baerns, Oxidative coupling of methane in the
gas phase. Kinetic simulation and experimental verification,
Ind. Eng. Chem. Res. 29 (1990) 2–10.
[4] M. Baerns, K. van der Wiele, J.R.H. Ross, Catal. Today 4 (1989)
471.
219
[5] J.A. Labinger, Quimica (1993) 48.
[6] M. Belgued, H. Amariglio, P. Pareja, A. Amariglio, J. Saint-Just,
Catal. Today 13 (1992) 437.
[7] T. Koerts, R.A. van Santen, New Frontiers in Catalysis, in: L.
Guczi, et al., (Eds.), Proc. 10th Int. Congress on Catalysis,
Elsevier, Amsterdam, 1993, p. 1065.
[8] M. Belgued, A. Amariglio, P. Pareja, H. Amariglio, J. Catal. 159 (1996)
441.
[9] F. Solymosi, A. Erdöhelyi, J. Cserenyi, Catal. Letters 16 (1992)
399.
[10] L. Guczi, R.A. van Santen, K.V. Sarma, Catal. Rev., Sci. Eng. 38 (1996)
249.
[11] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Methane conversion
using dielectric barrier discharge: comparison with thermal
process and catalyst effects, J. Nat. Gas Chem. 15 (2006) 87–92.
[12] A. Holmer, O. Olsvik, O.A. Rokstad, Fuel Process. Technol. 42 (1995)
249.
[13] Y. Yang, Direct non-oxidative methane conversion by
non-thermal plasma: experimental study, Plasma Chem.
Plasma Process (2003) 23.
[14] S.S. Kim, H. Lee, B.K. Na, H.K. Song, Reaction pathways of
methane conversion in dielectric-barrier discharge, Korean J.
Chem. Eng. 20 (2003) 869–872.
[15] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Kinetic modeling of
plasma methane conversion using gliding arc plasma, J. Nat.
Gas Chem. 14 (2005) 13–21.
[16] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Effect of additive gases on
methane conversion using gliding arc discharge, Energy 31 (2006)
2650–2659.
[17] M. Frenklach, Reaction mechanism of soot formation in
flames, Phys. Chem. Chem. Phys. 4 (2002) 2028–2037.
[18] K. Thanyachotpaiboon, S. Chavadej, T.A. Caldwell, L.L. Lobban,
R.G. Mallinson, Conversion of methane to higher hydrocarbons
in AC nonequilibrium plasmas, AIChE J. 44 (1998) 2252–2257.
[19] G.-B. Zhao, S. John, J.-J. Zhang, L. Wang, S. Muknahallipatna, J.C.
Hamannb, J.F. Ackerman, M.D. Argyle, O.A. Plumb, Methane
conversion in pulsed corona discharge reactors, Chem. Eng. J.
125 (2006) 67–79.
[20] M. Kraus, W. Egli, K. Haffner, B. Eliasson, U. Kogelschatzb, A.
Wokaun, Investigation of mechanistic aspects of the catalytic
CO2 reforming of methane in a dielectric-barrier discharge
using optical emission spectroscopy and kinetic modeling,
Phys. Chem. Chem. Phys. 4 (2002) 668–675.
[21] H.S. Kim, S.J. Oh, A study of the synthesis of C2-hydrocarbons
using methane activation, J. Ind. Eng. Chem. 4 (1998) 12–18.
[22] H.K. Jeong, S.C. Kim, C. Han, H. Lee, H.K. Song, B.K. Na,
Conversion of methane to higher hydrocarbons in pulsed DC
barrier discharge at atmospheric pressure, Korean J. Chem.
Eng. 18 (2001) 196–201.
[23] K.V. Kozlov, K. Michel, H.E. Wagner, Synthesis of organic
compounds from mixtures of methane with carbon dioxide in
dielectric-barrier discharges at atmospheric pressure, Plasma
Polymer. 5 (2000) 129–150.
[24] T.V. Choudhary, E. Aksoylu, D.W. Goodman, Nonoxidative
activation of methane, Catal. Rev. 45 (2003) 151–203.