Professional Documents
Culture Documents
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Clean Technology Research Center, Korea Institute of Science and Technology,
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School Environmental Resources Development, Asian Institute of Technology,
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Address: Clean Technology Research Center, Korea Institute of Science & Technology,
Phone: +82-10-2296-3748
Email: indarto_antonius@yahoo.com
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Abstract- Methane conversion by plasma offers a promising route to produce higher
basis of chemical reaction and products. In this paper, we present a method to obtain
the kinetic rate coefficient (k) from the experimental data. Although plasma reaction
by plasma could initiate coupling reactions and produce C2H6, C3H8, and C4H10.
Dehydrogenation of C2H6 into C2H4 and then to C2H2 could be clearly seen by the
higher value of the reaction rate constant of C2Hn+2 to C2Hn-2. Using the rate constant
values (k) obtained by this method, the pathways of the methane conversion by a
1. Introduction
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
There are mainly three approaches to converting CH4 into higher hydrocarbons in a
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high temperature process: the direct oxidative methane conversion (OMC), the
Fischer–Tropsch process via syngas, and the non-oxidative methane conversion [1].
Over the last decades, many researches have mainly focused on oxygen-containing
methanol [2]. In the presence of oxygen, the direct CH4 conversion to C2H6, C2H4 (one
of the most important raw materials in industrial production cycles), C 3Hn, C4Hn is
been investigated extensively [3,4] and is still most frequently used due to its higher
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 OCM is its low selectivity towards C2+, because
numerous amounts of solid carbon and hydrogen [11] with less C2+ production. Higher
hydrocarbon production via methyl coupling reactions occurred only with very short
towards C2+ products [11,13]. The reason for focusing on oxygen-free methane
enhancing the CH4 conversion and the C2+ yield, respectively. The optimization of the
NOPCM necessitates a detailed knowledge of the gas-phase reactions that occur and
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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 transformation
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
temperature (c.a. 25oC). The presented kinetic model is a part of efforts encompassing
Figure 1
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.
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A high frequency alternating current (AC) power supply with maximum voltage of
20kV was connected to the electrodes. The supplied power to the reactor was
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
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%. Those gases were provided by Kogas Corp.
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 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.
moles of C x H y converted
Conversion of C x H y = × 100 (1)
moles of initial C x H y
moles of C m H n produced
Concentration of C m H n = × 100 (2a)
total moles products
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m × moles of C m H n produced
Selectivity of C m H n = × 100
moles of C x H y converted (2b)
possible compounds that exist in the products or the reactants was calculated. The
pure compound to the reactor. Then, the product distribution was calculated and the
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 that the reaction will occur in 1st order reaction, the calculation
dCi n n
= −∑ k ij Ci + ∑ k ji C j (3)
dt j=1 j=1
where n is the maximum value of i and j for k-set which is 8 and kij denotes the
reaction rate constant of i molecule converts into specific j molecule. The assumption
was chose to simplify the calculation and make the data comparable each other. The
By solving Eq. 4, the calculation will result a set of kinetic rate constant (k) which can
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be arranged as:
0 k 12 k 18
k 21 0 k 28
k=
(5)
k 81 k 87 0
The value of k was obtained by an error minimization between model data and
experimental data. In this particular case, the minimization calculation was done
Eq. 4 using ‘ode23s’. The uniqueness of the result was measured by calculating the
mean-squared error of each set value of kij obtained from eight different input gases
∑ (k − k )
2
i
s= (6)
n −1
where n is the maximum size of k-set which is eight, k is the mean value of k-set.
Table 1
In order to obtain the rate constant k in Eq. 5, eight hydrocarbon gases: CH4, C2H2,
C2H6, C3H6, C3H8, iC4H10, and nC4H10 were introduced separately to the plasma
reactor at atmospheric pressure (~1 atm) and room temperature (~25oC). The flow rate
and supplied power were maintained similar at 30 ml/min and 60 Watt, respectively.
These values were obtained from the optimization of the previous research [14] in
order to avoid large amount of unknown products and carbon deposition which were
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difficult to measure.
Fragmentation reactions of methane into smaller molecules were more favorable than
synthesis reactions of higher hydrocarbons at lower input flow rates and higher
supplied power [11,15,16]. As higher hydrocarbons are more useful and valuable
products, increasing flow rates and lowering supplied power can be the way to avoid
above problems.
Table 1 shows the conversion rate of input gas and the distribution of products after
treated by dielectric barrier discharge at flow rate of 30 ml/min and supplied power of
60 W. Except for the experiments initiated by C2H2 (run 2) and C3H6 (run 5), the total
C and H atom balance between the reactants and products of all plasma process
reactants to the products were almost perfectly identified. Small amounts of carbon
deposition on the wall and inner electrode were found but, as the values were
achievement, since to obtain correct calculation of the kinetics, the C and H balance
between reactants and products should be equal. In the case when C 2H2 and C3H6 were
used as the reactant, the reaction produced a lot of solid carbon and/or soot. We could
not confirm whether the solid product was coming from the polymerization of C2H2
and C3H6 or agglomeration of monomolecular carbon. However, C2H2 and C3H6 are
From table 1, it can be figured out that when methane was the reactant, the products
were dominated by ethane (C2H6), with selectivity of 37.5%, propane (C3H8), 25.6%,
and butane (normal- and iso-C4H10), 25.4%. This product composition has a similarity
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with Thanyachotpaiboon et al.[18] result, used DBD system and AC power supply
similar to ours, with slightly higher selectivity of propane and butane. The higher
value of the selectivity was due to the use of a different method in the selectivity
which also suggested by Zhao et al.[19]. Abundant amounts of methyl radical could
hydrocarbons [20].
In the case of other products, e.g. acetylene and ethylene, those compounds could be
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
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2 C2H2 + 3 H2 n-C4H10 (10)
In order to supply H2, fragmentation of C2H2 as the intermediate reaction was needed.
C2H2 2 C + H2 (11)
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
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
In the case of C3H6 consumption process, the reactions occurred by two main parallel
ways:
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
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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%,
C3H6 produced from Eq. 16 could be suffered from reverse reaction of n-C4H10
formation
In this case, the probability of Eq. 17 is higher than Eq. 16 as high concentration of H 2
was found in the product stream. Moreover, coupling reaction of ׃CH2 diradical could
Taken from all above explanation, the reaction pathways of methane conversion in a
dielectric-barrier discharge at flow rate of 30 ml/min and supplied power of 60W are
shown in Figure 2.
Figure 2
4. Kinetic model
Table 2
In order to quantify the rate of the reaction, a kinetic model 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
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exploiting ‘ode23s’ to solve a set of differential equations in Eq. 4. The reaction rate
calculated values and the experimental results using ‘fminsearch’ module. The
estimated reaction rate constants (k) are listed in Table 2. Higher k value means the
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 (CH4C2H4) and k12 (CH4C2H2) shows that acetylene and
ethylene was not coming from the direct methane conversion. Losing two H’s and
coupling with another triplet ׃CH2 to form ethylene or losing three Hs and coupling
with duplet ·CH required many steps. There was also a possibility of attack by other
species before completing the radical coupling reaction. Acetylene and ethylene were
C2H6, occurred in the plasma reaction, could be detected by k43 (C2H6C2H4), 1.03
min-1, then k32 (C2H4C2H2), 1.79 min-1. The trend of the result was similar to Jeong
et al. [22] which also suggested by Kozlov et al. [23] that pathways of C2
The above stepwise dehydrogenation reaction was also identified in the thermal
confirmed by higher value of kx8, >0.5 min-1, except for methane. This result could
answer the high yield production of C4 compounds that usually produced in DBD
using AC power supply. This result confirmed the previous research that the addition
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the selectivity of butane [18]. Later on, intermolecular transformation of n-butane to i-
hydrocarbons (acetylene and ethylene) confirms 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,
of i-butane could be formed from C3 compounds, k58 = 0.54 min-1 and k68 = 0.7 min-1.
2.54 min-1, we have to consider the conversion comparison between n-butane and i-
butane. The conversion rate of i-butane is 10% lower than that of n-butane means that
The reverse reaction to produce methane was mostly coming from acetylene,
confirmed by k21 (1.31 min-1) which is higher than for other reactants. From this data,
we are also able to determine that the decomposition of higher hydrocarbons will not
produce CH4 as the product but instead will produce ·CH3, ׃CH2, or ·CH. The
existence of C1 radical hydrocarbons could help to increase the selectivity of C2, C3,
counting the tendency of the reaction pathway, the presence of intermediate species
By taking only the important and significant k values, we can draw a global reaction
pattern diagram of methane conversion (presented in Fig. 2). It shows that C2H4 has
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an important role as a branching agent to diversify the reaction mechanism. This idea
is supported by the data because C2H4 was easier to produce than other C2 compounds
from the cracking of higher hydrocarbons (C3 and C4). To form C2H6, the reactions
should be terminated by recombination reaction with H2. On the other hand, C2H2
Instead of dehydration reaction into C2H2, coupling reaction of C2H4 could form n-
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 60W. As shown in Figure 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
Conclusions
of 60W was studied. It shows that C2H4 has an important role on the global
mechanism, having function as a branching molecule which able to diverse the global
dehydrogenation of C2H6 was 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 long-chain molecule (normal- form). Using this method
which is relatively simple, the pathway pattern of CH4 conversion could be obtained.
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It will be a good advantage to predict or optimize the end products of direct methane
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
References
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[13] Yang, Y., 2003. Direct non-oxidative methane conversion by non-thermal plasma:
[14] Kim, S.S., Lee, H., Na, B.K., Song, H.K., 2003. Reaction pathways of methane
[15] Indarto, A., Choi, J.W., Lee, H., Song, H.K., 2005. Kinetic modeling of plasma methane
conversion using gliding arc plasma. J. Natur. Gas Chem. 14, 13-21.
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Ackerman, J.F., Argyle, M.D., Plumb, O.A., 2006. Methane conversion in pulsed corona
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discharge reactors. Chem. Eng. J. 125, 67-79.
[20] Kraus, M., Egli, W., Haffner, K., Eliasson, B., Kogelschatzb, U., Wokaun, A., 2002.
[21] Kim, H.S., Oh, S.J., 1998. A study of the synthesis of C 2-hydrocarbons using methane
[22] Jeong, H.K., Kim, S.C., Han, C., Lee, H., Song, H.K., Na, B.K., 2001. Conversion of
[23] Kozlov, K.V., Michel, K., Wagner, H. E., 2000. Synthesis of organic compounds from
[24] Choudhary, T.V., Aksoylu, E., Goodman, D.W., 2003. Nonoxidative activation of
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CH MF Bubble
CH 4 AC flow
C
power
suppl meter
y
Plasm
a
Reacto
r
G
C
19
i-C4H10
C3H8 C3H6
CH4 C2H6 C2H4
C2H2 n-C4H10
20
50
40 Experimental
Selectivity (%) Model
30
20
10
0
H4 H6 H6 H8 10 10
C2 C2 C3 C3 4H 4H
i- C n- C
Compounds
binary mixture methane + acetylene at the flow rate of 30 ml/min and supplied power
of 60 W.
21
A
n moles of C m H n produced
[1] selectivity of C m H n = ×
Note: The calculation of H balance includes the H2 in the output and the selectivity of component follows: 4 moles of CH 4 converted . All
data were obtained at flow rate of 30 ml/min and supplied power of 60 Watt.
E
A
j
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 )
i
(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 )
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-1; the standard deviation values inside the
parenthesis are in % unit.
ABIC