Kinetic modeling of plasma methane conversion in a dielectric barrier discharge

Shortened title: Kinetic of plasma methane conversion

Antonius Indarto1,2,*, Nowarat Congwanitwong2, Jae-Wook Choi1, Hwaung Lee1,

Hyung Keun Song1

1
Clean Technology Research Center, Korea Institute of Science and Technology,

PO Box 131, Cheongryang, Seoul, Korea

2
School Environmental Resources Development, Asian Institute of Technology,

PO Box 4, Klong Luang, Pathumthani, Thailand

1
Address: Clean Technology Research Center, Korea Institute of Science & Technology,

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

Phone: +82-10-2296-3748

Email: indarto_antonius@yahoo.com

2
Abstract- Methane conversion by plasma offers a promising route to produce higher

value of higher hydrocarbon products. As plasma reaction is relatively complex, a

kinetic modeling is required to get a general pattern of their complex interaction in

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

values obtained by this method, the pathways of the methane conversion by a

dielectric barrier discharge can be drawn.

Keywords: Plasma, dielectric barrier discharge, methane, kinetic reaction

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

gas). Thus, transportation of the stranded gas to consumers requires low-temperature

liquefaction (liquefied natural gas) or local conversion to liquid hydrocarbons. The

use of natural gas as a feedstock in chemical and pharmaceutical industry is an

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

resources but also a growing problem in view of the greenhouse effect.

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,

either indirect ones as in the Fischer–Tropsch processes or direct ones as in the

oxidative methane conversion. In the Fischer–Tropsch processes, CH4 is converted

into hydrocarbons, via synthesis gas, which is subsequently hydrogenated, e.g., to

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

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].

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

considerable amounts of CH4 are consumed forming CO and CO2. In contrast to

OCM, 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 reactions was occurred only in very

short time and high temperature 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

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

encompassing the oxygen-free surface chemistry. Based on the comparison between

the experimental and simulation data, the model was satisfied approaching the real

experimental result. The constructed model was applicable for the plasma reaction at

atmospheric pressure and ambient temperature.

Experimental setup and algorithm

Figure 1

5
The schematic diagram of experimental setup is shown in Figure 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 maximum voltage of

20kV was connected to the electrodes. The supplied power to the reactor was

maintained constant at 60W, measured by a watt meter (Metex model M-3860M).

In order to maintain the similarity of the reactor configuration, 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 at the range of

9.0-10 pF in ambient air condition.

2.2. Input gas and measurement system

All experiments were carried out by introducing eight different hydrocarbon

gases: CH4 (purity >99.99%), C2H2, C2H4, C2H6, C3H6, C3H8, i-C4H10, n-C4H10. Gas

Chromatography (YoungLin M600D, column: 30ft of Hayesep D) has been used to

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

measure the flow difference of products before and after reaction.

The products concentration and reactants conversion were formulated as:

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

2.3. Model algorithm

In this kinetic model, the possibility of molecule transformation to any

possible compounds that exist in the product or reactant was calculated. The reaction

rate of specific molecule hydrocarbon was measured experimentally by injecting

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

compound will follow:

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

employing Matlab sub-routine module ‘fminsearch’ after simultaneous integration of

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

which is expressed as:

∑ (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.

Results and discussion

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

be measured. Fragmentation reactions of methane into smaller molecules were more

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

way to avoid above problem.

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

to the products could be obtained almost complete. Relatively small amounts of

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

produced a lot and it will be discussed later.

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

supplied power, the probability to synthesis of higher hydrocarbons from methane

9
was higher than that at lower flow rate and higher supplied power (compared to the

result of [14]). Higher ethane selectivity could be obtained by coupling reaction of

methyl radical. Abundant amounts of methyl radical can combine with C2 molecules

to form C3 hydrocarbons or with C3 to form C4.

In the case of other products, e.g.: acetylene and ethylene, those compounds can be

form due to dehydrogenation of ethane. The tendency of acetylene formation from

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%).

Those products are required hydrogen to be formed from acetylene.

C2H2 + 3 H2  2 CH4 (7)

C2H2 + H2  C2H4 (8)

4 C2H2 + H2  i-C4H10 (9)

4 C2H2 + H2  n-C4H10 (10)

In order to supply H2, fragmentation reaction of C2H2 as intermediate reaction was

needed.

C2H2  2 C + H2 (11)

This reaction 11 was supposed to be occurred as total C atom of gaseous products

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.

Instead of dehydrogenation reactions of C2 hydrocarbons, coupling reaction was also

occurred simultaneously. Coupling reaction of C2 compounds will form butane in

which the long chain type (n-C4H10) was much favorable than the iso type (i-C4H10).

C2H4 + C2Hx + (8-x)/2 H2  n-C4H10 (12)

In the case of C3H6 compounds, the reactions occurred by two main parallel ways:

C3H6 + H2  C3H8 (13)

C3H6  C2H4 + C + H2 (14)

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.

Reversely, C3H6 could be formed by dehydrogenation of C3H8 or fragmentation of i-

C4H10. When C3H8 and i-C4H10 were the reactant, the selectivity of C3H6 reached 40%

and 20%, respectively. The proposed reactions mechanism follows:

C3H8  C3H6 + H2 (15)

i-C4H10  C3H6 + CH4 (16)

i-C4H10  C3H6 + CH2 + H2 (17)

C3H6 produced from Eq. 16 could be suffered from reverse reaction of n-C4H10

formation

C3H6 + CH4  n-C4H10 (18)

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

form C2H4 as its selectivity reached 14%.

CH2 + CH2  C2H4 (19)

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

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 using

‘fminsearch’ module which compared the calculated values and the experimental

results. The estimated reaction rate constants are listed in Table 2. Higher k value

means the reactant was rapidly reacting to produce products.

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 (CH4C2H4) and k12 (CH4C2H2) 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 (C2H6C2H4) then k32

(C2H4C2H2). The tendency of the result was similar to Jeong et al. [17] which also

suggested by Kozlov et al. [18] that pathways of C2 dehydrogenation reactions will

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

dehydrogenation reaction to remove two hydrogen atoms. Instead of dehydration

reaction into C2H2, coupling reaction of C2H4 could form n-C4H10 (Eq. 12) or reach

13
with CH2 radical to form C3H8.

Conclusions

The kinetics of methane conversion in a dielectric barrier discharge at supplied power

of 60W was studied. It shows that C2H6 has an important role on the global

mechanism. Dehydrogenation of C2H6 will produce C2H4 then continued by formation

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

of direct methane conversion by a dielectric barrier discharge.

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 study period in Torino, Italy.

References

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processes. Fuel Process. Technol. 42, 65-83.

[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.

[5] Labinger, J.A., 1993. Quimica 48.

[6] Belgued, M., Amariglio, H., Pareja, P., Amariglio, A., Saint-Just, J., 1992. Catal.

Today 13, 437.

[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

dielectric barrier discharge: comparison with thermal process and catalyst

effects. J. Natur. Gas Chem. 15, 87-92.

[12] Holmer, A., Olsvik, O., Rokstad, O.A., 1995. Fuel Process. Tech. 42, 249

[13] Yang, Y., 2003. Direct non-oxidative methane conversion by non-thermal

plasma: experimental study. Plasma Chem. Plasma Process. 23.

[14] Kim, S.S., Lee, H., Na, B.K., Song, H.K., 2003. Reaction pathways of methane

conversion in dielectric-barrier discharge. Korean J. Chem. Eng. 20, 869-872.

[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

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 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.

Conversion of methane to higher hydrocarbons in pulsed DC barrier discharge at

atmospheric pressure. Korean J. Chem. Eng. 18, 196-201.

[18] Kozlov, K.V., Michel, K., Wagner, H. E., 2000. Synthesis of organic compounds

from mixtures of methane with carbon dioxide in dielectric-barrier discharges at

atmospheric pressure. Plasma Polymer. 5, 129-150.

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Gas Bubble
MFC AC power flow meter
supply

Plasma
Reactor

GC

Figure 1. Schematic diagram of experimental set up

17
 i-C4H10
C3H8 C3H6
CH4 C2H6 C2H4
C2H2 n-C4H10

Figure 2. The pathway reaction of methane conversion

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