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Procedia Engineering 148 (2016) 1130 – 1136

4th International Conference on Process Engineering and Advanced Materials

Chemical Kinetic Modeling of Methane Combustion

Nora Boukhalfaa,*
a
Chemistry Department, University of Batna 1, 05000, Algeria.

Abstract

In this work, we have developed a chemical kinetic modeling of methane combustion using a detailed kinetic mechanism
including 213 elementary reactions and 48 species from literature. The mathematical model consists of a system of coupled
ordinary differential equations resulting from kinetic rate laws. The solution is performed with a computer code in FORTRAN
language based on the numerical fourth order Runge-Kutta method. The results show that the kinetic model used predicts
efficiently the consumption of methane and oxygen as well as the production of water and carbon dioxide. However, the
predicted nitrogen oxide formation (atmospheric pollutant) was less than the observed value.

©
© 2016
2016TheTheAuthors.
Authors.Published
PublishedbybyElsevier
ElsevierLtd. This is an open access article under the CC BY-NC-ND license
Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016.
Peer-review under responsibility of the organizing committee of ICPEAM 2016
Keywords: modeling; methane; combustion; mechanism; elementary reaction

1. Introduction

Models play an important role in improving our understanding of combustion processes and are able to assist in
the design of advanced energy conversion devices [1]. Kinetic models have become useful in the analysis of
practical energy conversion systems such as the internal combustion engines. A review of chemical kinetic models
of hydrocarbon combustion is given by Westbrook et al. [2].
Methane combustion chemistry has been extensively studied, and is now rather well known. Bowman et al. [3]
has simulated the combustion of methane in a perfectly stirred reactor using a mechanism including 24 elementary
reactions, the kinetic mechanism used in their model failed to explain the experimental data especially under fuel-

* Corresponding author. Tel./Fax: +213 33 31 90 15

E-mail address:boukhalfa_nora@yahoo.fr

1877-7058 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016
doi:10.1016/j.proeng.2016.06.561
 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136 1131

rich conditions. Heap et al. [4] have proposed a mechanism with 100 elementary reactions including the NO
formation mechanism and have obtained good agreement with the measurements. However, none of the previous
models included the C2 Chemistry, which is known to be an important part of the methane oxidation scheme.
More detailed kinetic mechanism containing 213 elementary reactions and 48 species have been suggested by
Glarborg et al [5]. In this mechanism, more reactions have been incorporated such as the conversion of NHi species
to NO and N2, the HCN chemistry, the C2 chemistry and the reactions of CH2 and CH.
The main objective of this work is the application of a kinetic model to the analysis of the chemistry of methane-
air combustion flame using the detailed kinetic mechanism proposed by Glarborg et al [5] with the consideration of
stoichiometric conditions.

Nomenclature

A preexponential factor in Arrhenius rate constant

C concentration (mol/m3)
E0 activation energy in Arrhenius rate constant (Joule/mol)
k rate constant of elementary reaction
P pressure (atm)
R the ideal gas constant
t time of combustion (seconds)
T temperature (K).
x molar fraction
Grec letters
E the pre-exponential temperature exponent
- stoichiometric number
Superscripts
(e) reactant of an elementary reaction
(p) product of an elementary reaction
S number of reactants in an elementary reaction
Subscripts
s chemical species
r elementary reaction

2. Mathematical model

The chemistry of methane air combustion is analysed using the kinetic rate laws.
For an elementary reaction, r, given in the form,
S S

¦-
s 1
(e)
rs As o¦ - rs( p ) Bs
s 1
(1)

Where s is a chemical species and - rs and - rs

(e ) ( p)
denote the stoichiometric coefficients of reactants and products
respectively, the kinetic rate law of a species i in the elementary reaction r, is given by the expression [6]:
§ w Ci ·
 – C
S
-rs( e )
¨¨ ¸¸ k r -ri( p )  -ri( e ) (2)
© wt
s
¹r s 1
Where Ci is the concentration of a species, i , CS is the concentration of the reactant s.
For a kinetic reaction mechanism of methane-air combustion composed of 213 elementary reactions and 48
species given in the form,
S S

¦ -rs(e) As o¦ -rs( p ) Bs
s 1 s 1
;r 1,....., 213 , (3)
1132 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136

The kinetic rate law for a species i will be [6]:

§ w Ci ·
 – C
213 S
¨¨ ¸¸ ¦ k r -ri( p )  -ri(e) -rs( e )
; i 1,....., 48 (4)
© wt
s
¹ r 1 s 1
Where kr is the rate constant of an elementary reaction, r, it is calculated using the modified Arrhenius equation:
§ E ·
kr A T E exp¨  0 ¸ (5)
© RT ¹
The kinetic rate laws equations with the initial conditions can be put in the following form:

­ Ci Ci0 at t 0
°
® d Ci (6)
° dt Fi C1 , ....., C S , k1 , ....., k R  ; i 1,...., 48 for t 0
¯
2.1. Initial conditions

We consider in this work the case of combustion of a stoichiometric mixture at atmospheric pressure. The
overall reaction of methane-air combustion is written as:
CH4 + 2 O2 o 2 H2O +CO2
The air contains 78% of Nitrogen (N2), 20% of oxygen (O2) and 2% of Argon (Ar), the molar fraction of methane is
given by:
1
x CH4 (7)
1  5-O2
Thus, the initial mixture will contain the following stoichiometric proportions:
1 2 7.8 0.2
x CH 4 , x O2 , x N2 , x Ar
11 11 11 11
The initial concentrations are calculated using the following equation:
P
C i0 xi (8)
RT
Where Ci0 is the initial concentration of species i; P is the pressure; R is the ideal gas constant; T is Temperature;
and xi is the mole fraction of species, i. The combustion conditions considered in this work are: Pressure = 1atm and
temperature of methane flame = 2222K, thus the initial concentrations are:

C0CH4 = 0.498909 mol/m3; C0O2 = 0.997818 mol/m3; C0N2= 3.89174 mol/m3; C0Ar = 0.09978 mol/m3

The numerical solution is necessary to solve the system of modeling differential equations. The solution is
performed with a computer program using the fourth order Runge-Kutta method [7]. We have elaborated a computer
code in FORTRAN language for this purpose. The computation procedure is shown in Figure 1.
 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136 1133

Start

Input parameters:
A, β, T

Input initial conditions:

Ci0 (t=0)

Compute kr

Increment time:
t+Δt

Compute Ci applying the Subroutine

4th order Runge-Kutta for evaluating
method Fi

No
Permanent
mode ?

Yes
Print results :
Ci (t)

Stop

End
Fig.1. Algorithm of the computer code.

3. Results

We have used in this modeling work a kinetic mechanism including 213 elementary reactions and 48 species
from literature [5]. This mechanism includes a large number of elementary reactions such as the C2 chemistry, the
CH2 and CH chemistry and also the conversion of NHi species to NO and N2 and the HCN chemistry.
The mathematical model consists of a system of coupled ordinary differential equations resulting from kinetic
rate laws. The solution is performed using a computer code in FORTRAN language, which has been elaborated for
this purpose, based on the numerical fourth order Runge-Kutta method with a step of time equal to 10-9 seconds.
The computer code generates the concentrations of all the 48 species included in the kinetic mechanism used.
Some of the results are presented in figures 2-7. Figures 2 and 3 illustrate the total consumption of the main
reactants, methane and oxygen (CH4 and O2) after about 0.90 milliseconds.
Note that for the inetrmediate species such as radicals, H, CH3, CH2, CH, O,.., The results indicate the apparition
and the consumption of all these intermediate species during the time of the combustion.
1134 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136

Concentration of CH4 (mol/m )

0,6

3
0,5 CH4
0,4

0,3

0,2

0,1

0,0 -4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig.2. Time evolution of the concentration of CH4

1,2
Concentration of O2 (mol/m )
3

1,0 O2

0,8

0,6

0,4

0,2

0,0
-4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig. 3. Time evolution of the concentration of O 2

Figures 4 and 5 illustrate the production of the final products of methane combustion, carbon dioxide and water
(CO2 and H2O) after about one milliseconds.
Concentration of CO2 (mol/m )
3

0,30

0,25 CO2

0,20

0,15

0,10

0,05

0,00 -4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig. 4. Time evolution of the concentration of CO 2

 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136 1135

Concentration of H2O (mol/m )

3
1,4
1,2 H2 O
1,0
0,8
0,6
0,4
0,2
0,0 -4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig.5. Time evolution of the concentration of H2O.

The results show also the appearance of carbon monoxide (CO) (fig.6.), this is surely due to a partially
incomplete reaction. In fact, from experience, we know that the stoichiometric mixture of the reactants does not
involve necessarily a complete reaction, an excess of air is always necessary to complete the combustion.
Concentration of CO (mol/m )

1,0
3

0,8 CO

0,6

0,4

0,2

0,0 -4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig.6. Time evolution of the concentration of CO.

The formation of nitric oxide (NO) during the combustion of methane is illustrated in figure 7. As presented in
this figure, the nitric oxide appears after about 0.9 milliseconds with a very small concentration (6x10-6 mol/m3), this
value is much less than the observed NO levels by Fenimore [8] for methane flame.
The mechanism of nitric oxide formation from atmospheric nitrogen at flame temperature and near stoichiometric
conditions is undestrood by what is often called the extended Zeldovich reaction mechanism,

O + N2 → NO + N
N + O2 → NO + N
N + OH → NO + H

this mechanism, when coupled with other reactions that describe the oxidation of methane species and the formation
of atomic oxygen and the hydroxyl radical predicts nitric oxide concentrations. Note that these elementary reactions
have been also included in the kinetic mechanism used in this work.
As a consequence, we can say that the kinetic mechanism used in this work is not necessarily complete and more
elementary reactions could be added.
1136 Nora Boukhalfa / Procedia Engineering 148 (2016) 1130 – 1136

Concentration of NO (mol/m )
3
-5
1,8x10
-5
1,5x10 NO
-5
1,2x10
-6
9,0x10
-6
6,0x10
-6
3,0x10
0,0
-4 -3 -3 -3
0,0 5,0x10 1,0x10 1,5x10 2,0x10
Time (seconds)

Fig. 7. Time evolution of the concentration of NO.

4. Conclusion

In this modeling work, the chemistry of methane air combustion has been analysed using kinetic rate laws. A
detailed kinetic mechanism consisting of 213 elementary reactions and 48 chemical species from literature has been
used. This mechanism includes many reactions such as the oxidation mechanism of methane, the C2 Chemistry, the
HCN chemistry, the conversion of NHi species to NO and N2, the HCN chemistry and the reactions of CH2 and CH.
The mathematical model, resulting from kinetic rate laws, has been solved using a computer code in FORTRAN
language based on the numerical fourth order Runge-Kutta method.
The results show that the kinetic model used predicts efficiently the oxygen and methane consumption as well as
water and carbon dioxide production. However, the predicted nitrogen oxide formation was less than the observed
value.

References

[1] A.S. Tomlin, The role of sensitivity and uncertainty analysis in combustion modelling, Proceedings of the Combustion Institute 34 (2013)
159–176
[2] C.K. Westerbrook, F.L. Dryer,, Chemical kinetic modeling of hydrocarbon combustion, Prog. Energy Comb. Sci, 10 (1984) 1-57
[3] B.R. Bowman, D.T. Pratt, C.T. Crowe, Effects of turbulent mixing and chemical kinetics on nitric oxide production in a jet-stirred reactor,
Symp. (Int.) Comb. , 14 (1973) 819-830
[4] M.P. Heap, T.J.Tyson, J.E. Cichanowicz, R. Gershman, J. Kau, Environmental aspects of low Btu gas combustion, Symp. (Int.) Comb. , 16
(1977) 535-545
[5] P. Glarborg, J.A. Miller, R.J. Kee, Kinetic Modeling and Sensitivity Analysis of Nitrogen Oxide Formation in Well-Stirred Reactors,
Combust. and Flame 65 (1986) 177-202.
[6] J. Warnatz, U. Maas, R.W. Dibble. Combustion, physical and chemical fundamentals, modeling and simulation, experiments, pollutant
formation, Fourth ed, Springer-Verlag Berlin 2006.
[7] W.H. Press, B.P. Flannery, S. A. Teukolsky, W.T. Vetterling. Numerical Recipes, New york, 1986.
[8] C.P. Fenimore. Formation of nitric oxide in premixed hydrocarbon flames. Symp. (Int.) Comb. , 13 (1971) 373-380