1
Clean Technology Research Center, Korea Institute of Science and Technology,
2
School Environmental Resources Development, Asian Institute of Technology,
1
Address: Clean Technology Research Center, Korea Institute of Science & Technology,
Phone: +82-10-2296-3748
Email: indarto_antonius@yahoo.com
2
Abstract- Methane conversion by plasma offers a promising route to produce higher
these systems relatives to the chemical reaction and its products. In this paper, we
present an experimental method to obtain the kinetic rate coefficient of the reactions.
Although it was complex, the reaction gave a certain pattern on the reaction pathways.
When methane was decomposed, coupling reaction to produce C2H6, C3H8, and butane
was occurred. Dehydrogenation of C2H6 into C2H4 then continued to C2H2 could be
clearly seen by higher value of the rate constant of the reaction. Using rate constant
3
Introduction
Methane, the major component of natural gas, is widely distributed at sites around the
world. However, many of these sites are inaccessible by pipelines (stranded natural
alternative to crude oil whose supplies might run out in the next century. Moreover,
flaring gas, which is a permanent companion of all oil fields, could be used more
efficiently. So far, it is usually burnt to avoid explosions. This is not only a waste of
There are mainly three approaches to converting CH4 into higher hydrocarbons in
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, research has mainly focused on oxygen-containing processes,
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
4
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 was occurred only in very
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 occurring gas-phase and its kinetics.
In this work, we develop a kinetic for plasma methane and higher hydrocarbons. By
finding the kinetic constant of each reaction, the pathway of reaction could be drawn
easily. The model includes the gas-phase transformation of molecules that exist in the
reactant and products. The kinetic model presented here is part of these efforts
the experimental and simulation data, the model was satisfied approaching the real
experimental result. The constructed model was applicable for the plasma reaction at
Figure 1
5
The schematic diagram of experimental setup is shown in Figure 1. Details of each
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 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 at the range of
gases: CH4 (purity >99.99%), C2H2, C2H4, C2H6, C3H6, C3H8, i-C4H10, n-C4H10. Gas
analyze the quantitative amount of products which supported by flame ionized (TCD)
and thermal conductivity detector (TCD). Considering the volume expansion and the
6
compression of products, the output line was connected to a bubble flow meter to
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% (2)
total moles products
possible compounds that exist in the product or reactant was calculated. The reaction
single pure compound to the reactor. Then, the products distribution was calculated
and the rate of molecule transformation to other molecules could be obtained. In this
experiment, 8 hydrocarbons were existed in the plasma system, which are: (1) CH4,
(2) C2H2, (3) C2H4, (4) C2H6, (5) C3H6, (6) C3H8, (7) n-C4H10, and (8) i-C4H10. As we
assume that the reaction will follow 1st order reaction, the calculation of each
dC i n n
= −∑ k ij C i + ∑ 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 k ij denotes the
reaction rate constant of i molecule convert into specific j molecule. The value of kij
will be 0 if i=j.
7
dC1
dt k11 k18 C1 C8 k11 k 81 C1 C1
= − +
dC (4)
8 k 81 k 88 C1 C8 k18 k 88 C8 C8
dt
By solving Eq. 4, the calculation will result a set of kinetic constant which can be
arranged as:
0 k12 k18
k 0 k 28
21
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 by
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 8 different input gases
∑ (k − k )
n 2
i
σ= i =1
(6)
n −1
where n is the maximum size of k-set which is 8, k is the mean value of k-set.
Table 1
In order to obtain the rate constant k (Eq. 5), eight hydrocarbon gases: CH 4, C2H2,
8
C2H6, C3H6, C3H8, iC4H10, and nC4H10, existed in the product stream of methane
conversion using plasma, were introduced separately to the plasma reactor. The flow
rate and supplied power was maintained similar at 30 ml/min and 60 Watt,
respectively. This value was the optimization of the previous research [14] in order to
avoid the large amount of unknown products and carbon deposition which difficult to
favorable rather than higher hydrocarbons formation 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 powers could be the
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 C2H2 (run 2) and C3H6 (run 5), the total C and H atom of the products
after plasma conversion were close to 100% means that all of reactant transformation
carbon deposit on the wall and inner electrode were found and the value could be
neglected in the calculation. However, it was a good achievement when the C and H
balance was close to 100% in order to obtain correct calculation of the kinetics. In the
case when C2H2 and C3H6 were used as the reactant, solid carbon and/or soot was
From table 1, it can be figured out that when methane was the reactant, the products
were propane (C3H8), butane (n- and i-C4H10), and ethane (C2H6). The selectivity of
propane, n-butane, i-butane, and ethane reached 18.3%, 9.0%, 2.5%, and 54.4%,
respectively. It supports our previous statement that at higher flow rate and lower
9
was higher than that at lower flow rate and higher supplied power (compared to the
methyl radical. Abundant amounts of methyl radical can combine with C2 molecules
In the case of other products, e.g.: acetylene and ethylene, those compounds can be
ethylene and ethylene from ethane by dehydrogenation reactions was clearly seen
from run 4 of Table 1. When ethane was the reactant, the selectivity ethylene was
22.3% which is two times higher compared when acetylene was used as reactant. The
similar phenomenon was also occurred in the case of acetylene formation. The
selectivity of acetylene production reached 21.8% when ethylene was the reactant and
only 1.8% when methane was the reactant. An interesting phenomenon was occurred
when acetylene was used as the reactant which could be an important part to describe
the kinetic pathways. Acetylene will be converted mostly into methane, 24%, and at
the same time, it also produces ethylene (12%), i-butane (10%), and n-butane (12%).
needed.
C2H2 2 C + H2 (11)
10
which was only 52% compared to the total C atom of reactant. Numerous amount of
solid carbon was found and attached on the surface of the reactor wall and inner
electrode.
which the long chain type (n-C4H10) was much favorable than the iso type (i-C4H10).
In the case of C3H6 compounds, the reactions occurred by two main parallel ways:
From these two reactions, we can predict less amount of total C atom number in the
gaseous products due to carbon solid formation of Eq. 14 and it was proved that the
total C atom in the gaseous products was only 78% compared to the original reactant.
C4H10. When C3H8 and i-C4H10 were the reactant, the selectivity of C3H6 reached 40%
C3H6 produced from Eq. 16 could be suffered from reverse reaction of n-C4H10
formation
11
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 radical could
Concluded from the data in Table 1, the reaction pathways of methane in a dielectric-
barrier discharge at flow rate of 30 ml/min and supplied power of 60W are shown in
Figure 2.
Figure 2
Kinetic model
Table 2
In order to quantify the rate of the reaction, a kinetic model was built which follows
above algorithm. Some assumptions were used to reduce the complexity of the
reactions: (i) all the reactions follow first order; (ii) the formation of coke and
hydrogen was negligible in the model. All calculations were calculated using Matlab
‘fminsearch’ module which compared the calculated values and the experimental
results. The estimated reaction rate constants are listed in Table 2. Higher k value
From table 2, the value of k-set supports our previous statements that the
decomposition of methane will produce C2H6 (k14), C3H8 (k16), and C4 (k17 and k18).
12
Low value of k13 (CH4C2H4) and k12 (CH4C2H2) shows that acetylene and etylen
was not coming from methane conversion. The dehydrogenation reactions of C2H6
which occurred in the plasma reaction could be detected by k43 (C2H6C2H4) then k32
(C2H4C2H2). The tendency of the result was similar to Jeong et al. [17] which also
follow:
CH 4 → C2 H 6 → C2 H 4 → C2 H 2
However, n-butane hydrocarbon formation which comes from C2H6 can be confirmed
by higher value of k48 than other kx8 values. The formation of i-butane from C3
compounds was presented by k58 and k68. Reverse reactions of methane production,
which is mostly coming from C2H2, can be confirmed by k21 which higher than other
reactants.
Following the combination of k values, it shows that C2H4 has an important role on
the pathway traffic of methane conversion (Fig. 2). It is understandable caused C2H4
was easier to be produced 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 formation requires further
reaction into C2H2, coupling reaction of C2H4 could form n-C4H10 (Eq. 12) or reach
13
with CH2 radical to form C3H8.
Conclusions
of 60W was studied. It shows that C2H6 has an important role on the global
of C2H2. Coupling reaction of C2H6 with C2 hydrocarbons would result butane which
usually long chained type. Decomposition of butane could form C3 compounds. Using
this method which is relatively simple, the pathway pattern of CH4 conversion could
be obtained easily. It will be a good advantage to predict or optimize the end products
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
[1] Gradassi, M.J., Green, N.W., 1995. Economics of natural gas conversion
[2] Bell, A.T., 1984. Mechanisms of Fischer-Tropsch synthesis, in: NTiS report
14
number: DE84014608.
[3] Zanthoff, H., Baerns, M., 1990. Oxidative coupling of methane in the gas phase.
Kinetic simulation and experimental verification. Ind. Eng. Chem. Res. 29, 2-10.
[4] Baerns, M., van der Wiele, K., Ross, J.R.H., 1989. Catal. Today 4, 471.
[6] Belgued, M., Amariglio, H., Pareja, P., Amariglio, A., Saint-Just, J., 1992. Catal.
[7] Koerts, T., van Santen, R.A., 1993, New frontiers in catalysis, in: Guczi, L., et
al. (Eds.), Proc. 10th Int. Congress on Catalysis. Elsevier, Amsterdam, p. 1065.
[8] Belgued, M., Amariglio, A., Pareja, P., Amariglio, H., 1996. J. Catal. 159, 441.
[9] Solymosi, F., Erdöhelyi, A., Cserenyi, J., 1992. Catal. Lett. 16, 399.
[10] Guczi, L., van Santen, R.A., Sarma, K.V., 1996. Catal. Rev. Sci. Eng. 38, 249.
[11] Indarto, A., Choi, J.W., Lee, H., Song, H.K., 2006. Methane conversion using
[12] Holmer, A., Olsvik, O., Rokstad, O.A., 1995. Fuel Process. Tech. 42, 249
[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.
[16] Indarto, A., Choi, J.W., Lee, H., Song, H.K., 2006. Effect of additive gases on
15
methane conversion using gliding arc discharge. Energy 31, 2650-2659.
[17] Jeong, H.K., Kim, S.C., Han, C., Lee, H., Song, H.K., Na, B.K., 2001.
[18] Kozlov, K.V., Michel, K., Wagner, H. E., 2000. Synthesis of organic compounds
16
Gas Bubble
MFC AC power flow meter
supply
Plasma
Reactor
GC
17
i-C4H10
C3H8 C3H6
CH4 C2H6 C2H4
C2H2 n-C4H10
18
Table 1. The reactant conversion and products distribution of plasma process
Products concentration [ %]
Run Reactan
CH4 C2H2 C2H4 C2H6 C3H6 C3H8 iC4H10 nC4H10
1 CH4 86.20 0.17 0.45 2.04 0.00 0.93 0.26 0.43
2 C2H2 3.02 91.95 1.45 0.00 0.14 0.00 0.00 0.28
3 C2H4 2.67 3.31 84.30 0.68 0.38 0.67 0.67 1.84
4 C2H6 0.96 1.27 2.10 90.57 0.16 0.89 0.05 0.85
5 C3H6 0.70 0.90 1.48 0.46 90.16 1.23 0.99 0.57
6 C3H8 2.31 0.47 2.03 0.95 2.54 88.27 0.09 0.00
7 iC4H10 2.36 2.35 4.02 1.65 3.19 1.39 83.33 5.94
8 nC4H10 1.27 1.08 2.29 1.28 1.36 1.46 2.33 91.63
Note: data was obtained at flow rate of 30 ml/min and supplied power of 60 Watt.
19
Table 2. reaction rate coefficient (k)
j
kij
1 2 3 4 5 6 7 8
1 0.00 0.06 0.18 0.50 0.02 0.30 0.13 0.29
2 1.31 0.00 0.17 0.18 0.31 0.06 0.14 1.47
3 0.08 1.79 0.00 0.01 0.22 0.02 0.25 1.01
4 0.11 0.30 1.03 0.00 0.07 0.67 0.15 0.94
i
5 0.09 0.23 0.33 0.14 0.00 0.53 0.54 0.53
6 0.06 0.97 0.16 0.49 0.48 0.00 0.70 0.97
7 0.06 0.67 1.28 0.89 1.28 1.45 0.00 2.45
8 0.74 1.07 2.27 0.39 1.05 0.33 1.38 0.00
Note: 1. CH4; 2. C2H2; 3. C2H4; 4. C2H6; 5. C3H6; 6. C3H8; 7. i-C4H10; 8. n-C4H10. The value of kij refers to the value of reaction rate coefficient of molecule i to molecule j.
20