Kinetic modeling of plasma methane conversion in a dielectric barrier discharge

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-added products. As plasma reaction is relatively complex process, kinetic

modeling is necessary to obtain a general pattern of the complex interaction on the

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

was classified as chemically complex interaction, the reactions showed a certain

pattern of the mechanism. In pure methane injection, the decomposition of methane

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

dielectric barrier discharge can be drawn.

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

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

products, for example acetylene and ethylene.

There are mainly three approaches to converting CH4 into higher hydrocarbons in a

3
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

processes, either indirect ones as in the Fischer–Tropsch process 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].

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 occurred only with 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 gas-phase reactions that occur and

4
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

dielectric barrier discharge at atmospheric pressure (c.a. 1 atm) and ambient

temperature (c.a. 25oC). The presented kinetic model is a part of efforts encompassing

the oxygen-free plasma chemistry for methane conversion.

2. Experimental setup and algorithm

Figure 1

The schematic diagram of the 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.

5
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 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%. Those gases were provided by Kogas Corp.

(Korea Gas Corp.). A Gas Chromatography (YoungLin M600D, column: 30ft 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 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 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

6
 m × moles of C m H n produced
Selectivity of C m H n = × 100
moles of C x H y converted (2b)

2.3. Model algorithm

In the kinetic model, the possibility of molecular transformation 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 that the reaction will occur in 1st order reaction, the calculation

of each compound is as follows:

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

value of kij will be 0 if i=j.

 dC 1 
 dt  = − k 11  k 18  C 1  C 8  + k 11  k 81  C 1  C1 
       
                 
        (4)
  k 81  k 88  C 1  C 8  k 18  k 88  C 8  C 8 
 dC 8 
 dt 

By solving Eq. 4, the calculation will result a set of kinetic rate constant (k) which can

7
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

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 eight different input gases

which is expressed as:

∑ (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.

3. Results and discussion

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

8
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

approximately closed to 100% which means that the molecular transformation of

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

relatively small, those could be neglected in the calculation. It was a good

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

well-known as soot precursor in the pyrolysis or combustion process [17]. In this

case, the similar phenomenon is likely occurred in the plasma process.

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

9
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

calculation. Thanyachotpaiboon 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 dehydrogenation reaction 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 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.

C2H2 + 3 H2  2 CH4 (7)

C2H2 + H2  C2H4 (8)

2 C2H2 + 3 H2  i-C4H10 (9)

10
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

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.

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

In the case of C3H6 consumption process, the reactions occurred by two main parallel

ways:

C3H6 + H2  C3H8 (13)

C3H6  C2H4 + C + H2 (14)

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

11
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:

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)

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

form C2H4, as its selectivity reaches 14%, follows [21]:

CH2 + CH2  C2H4 (19)

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

12
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

estimated 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 (CH4C2H4) and k12 (CH4C2H2) 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

formed by stepwise dehydrogenations of ethane. The dehydrogenation reactions of

C2H6, occurred in the plasma reaction, could be detected by k43 (C2H6C2H4), 1.03

min-1, then k32 (C2H4C2H2), 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

dehydrogenation reactions will follow:

CH 4 → C2 H 6 → C2 H 4 → C2 H 2

The above stepwise dehydrogenation reaction was also identified in the thermal

coupling of methane [24].

Interestingly, n-butane hydrocarbon could be formed from any hydrocarbons species,

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

of higher hydrocarbons, e.g. ethane, on plasma methane conversion would increase

13
the selectivity of butane [18]. Later on, intermolecular transformation of n-butane to i-

butane occured 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) 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,

will produce double C2 molecules or even more if it decomposed to C1 molecules.

Instead of coming from the intermolecular transformation 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 to n-butane, by k78 =

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

i-butane is more stable than n-butane.

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,

and C4 compounds by coupling reactions. Unfortunately, as this method is just

counting the tendency of the reaction pathway, the presence of intermediate species

could not be confirmed scientifically.

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

14
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

formation required 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 react with CH2 radical to form C3H6.

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

of methane and/or hydrocarbon conversion.

Conclusions

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

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

reaction mechanism. Similar to thermal methane decomposition reaction,

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.

15
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 did not cover 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 study period in Turin, Italy.

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1998. Conversion of methane to higher hydrocarbons in AC nonequilibrium plasmas.

AIChE J. 44, 2252-2257.

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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.

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18
CH MF Bubble
CH 4 AC flow
C
power
suppl meter
y
Plasm
a
Reacto
r

G
C

Figure 1. Schematic diagram of experimental set up.

19
 i-C4H10
C3H8 C3H6
CH4 C2H6 C2H4
C2H2 n-C4H10

Figure 2. The pathway reaction of methane conversion.

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

Figure 3. The comparison between experimental and model simulation results of

binary mixture methane + acetylene at the flow rate of 30 ml/min and supplied power

of 60 W.

21
A

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

Conversion Products concentration [ %] Atom balance

Reactan [ 1]
[ %] CH4 C2H2 C2H4 C2H6 C3H6 C3H8 iC4H10 nC4H10 Cout/Cin Hout/Hin
CH4 13.8 86.20 0.17 0.45 2.04 0.00 0.93 0.26 0.43 0.95 1.01
C2H2 12.0 3.03 81.95 1.45 0.00 0.14 0.00 0.00 0.28 0.87 1.13
C2H4 15.7 2.67 3.31 84.30 0.68 0.38 0.67 0.67 1.84 0.95 0.98
C2H6 9.4 0.96 1.27 2.10 90.57 0.16 0.89 0.05 0.85 0.97 0.98
C3H6 9.8 0.70 1.60 2.48 0.46 80.16 2.23 0.99 0.57 0.89 1.01
C3H8 11.7 2.31 0.47 2.03 0.95 2.54 88.27 0.09 0.00 0.97 0.96
iC4H10 16.7 2.36 2.35 4.02 1.65 3.19 1.39 83.33 5.94 1.04 1.00
nC4H10 8.4 1.27 1.08 2.29 1.28 1.36 1.46 2.33 91.63 1.03 0.98

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.

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Table 2. reaction rate coefficient (k)

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