CHAPTER-7

Investigation of Kinetic Mechanisms

of Methane Oxidation

In this chapter, the combustion of methane was simulated using

four kinetic models of methane in CHEMKIN 4.1.1 for 0-D closed
internal combustion (IC) engine reactor.

Two detailed

(GRIMECH3.0 & UBC MECH2.0) and two reduced (One step &
Four steps) models were examined for various IC engine designs.
The detailed models (GRIMECH3.0, & UBC MECH2.0) and 4step models successfully predicted the combustion while global
model unable to predict any combustion reaction. This study
illustrated that the detailed model showed good concordances in
the prediction of chamber pressure, temperature and major
combustion species profiles. The detailed models were also
exhibited the capabilities to predict the pollutants formation in an
IC engine while reduced schemes showed failure in the prediction
of pollutants emissions. Although, there are discrepancies among
the profiles of four considered model, the detailed models
(GRIMECH3.0 & UBC MECH2.0) produced the acceptable
agreement in the species prediction and formation of pollutants.

186

7.1

Introduction:
Oxidation models of methane combustion, reported in the literature [Kaufman,

1982; Bowman et al, 2001; Frenklach et al, 1992; Peters, 1993 & 1985; Magel et al, 1996;
West brook, 1985; Glarborg et al, 1986; Miller, 1989; Konnov, 2000; Hughes et al, 2001;
Gregory et al; West Brook, 1981; Duterque et al, 1981; Hautmann et al, 1985; ] Jones et al,
1988; Tianfeng et al, 2005; Lavoie et al, 1970], were used to study methane
combustion/burning in furnaces, burners, bunsen flame burner, etc. Simulation of the CH4
combustion in an internal combustion engine is very important to the design of engine and
the control of air pollutants derived form the exhaust. One of the key objectives is to
establish a kinetic model, in which the pressure and temperature profile in the engine, and
the important reactants and products can be simulated.
In current study, consequences of the selected (detailed & reduced) models for the profiles
of temperature, pressure and major species produced are discussed. An appropriate model
which predicts combustion species like NOx, CO, CO2, and H2O, etc in engine combustion
chamber is identified. The simple criteria of comparing simulation results (profiles) of
detailed and reduced models as followed in study was described by Hemant, et al, 1996.

7.2

Implantation of Detailed and Reduced Kinetic Mechanism of

Methane Oxidation in IC engine:
In this study, we set our simulation starting crank angle to -142 degrees in the

software input. Other simulation parameters we used in the software simulation were cycles
end time as 0.043 sec or for 257 degrees crank angle to 115 degrees after TDC. The gas
mixture pressure and temperature at IVC are 107911 Pa (or 1.065 atm) and 550 K,
respectively. Following four mechanisms were investigated for methane combustion in
internal combustion engines as given in Table 7.1.

187

Table 7.1 Tested Mechanism of Methane Combustion

Sr.
No
1
2

3
4

Kinetic
Model
Type
Global One-Step
Reaction
Four Step
Reaction Models
of Jones and
Lindstedt

Reactions
CH4+2O

CO2+2H2O

Arrhenius Parameters
A

Ta(K)
1.50E+13 0.0
20000.0

(i) CH4+1/2O2 =

CO+2H2

4.40E+14

0.0

24000.0

(ii) CH4+H2O =

CO+3H2

3.00E+1

0.0

24000.0

2.50E+1
2.75E+12

-1.0
0.0

32000.0
16000.0

(iii) H2+1/2O2 = H2O

(iv) CO+H2O = CO2+H2

GRIMECH
3.0
(53
species
(available on Internet).
UBC MECH2.0 Kinetic mechanism
http://kbspc.mech.ubc.ca/kinetics.html.

&

325

available

on

reactions)
Internet

at

Where, A, , Ta (Ta= Ea/T) are the parameters for Arrhenius Law defined below;

k = AT e

Ea
RT

Two of these models are the detailed such as GRIMECH 3.0 & UBC MECH2.0 and other
two are reduced such as Duterque (Global One Step) & Jones and Lindstedt (Four Steps).
Two types of data files are required to input for execution of CHEMKIN module; (i)
Mechanism data files and (ii) thermodynamics data files.

Table 7.2
Detailed
Kinetic
Model

Important Species Considered in UBC MECH 2.0 and GRI MECH 3.0
Kinetic Models
No of
No of
Important Reacting Species/Intermediates
Species Reactions
(Radicals)

UBC
54

277

MECH2.0

GRI3.0

53

325

H2
H
O
O2
OH
H2O HO2 H2O2 C
CH
CH2
CH2(S) CH3
CH4
CO2 CO
CH2O CH2OH
CH3O CH3OH C2H C2H2 C2H3 C2H4 C2H5 C2H6
HCCO CH2CO HCCOH N2
AR CH3O2 CH3O2H
C2H5O C2H5O2 C2H5O2H CH3CO CH3CHO C2H4O C2H3O
C3H8 nC3H7 iC3H7 nC3H7O2 iC3H7O2 nC3H7O2H iC3H7O2H
nC3H7O iC3H7O C3H6 C3H5 C3H4 C2H4O2H
O
O2
OH
H2O HO2 H2O2 C
CH
CH2
CO2 HCO CH2O CH2OH
CH2(S) CH3 CH4 CO
CH3O CH3OH C2H C2H2 C2H3 C2H4 C2H5 C2H6
HCCO CH2CO HCCOH N
NH NH2 NH3 NNH
NO
NO2 N2O HNO CN
HCN H2CN HCNN
HCNO HOCN HNCO NCO N2 AR
C3H7 C3H8
CH2CHO

Some important species and reaction (pressure dependent) of both detailed models are
given in Table 7.2 to 7.4.
188

Table 7.3 Some Important Reactions of GRI MECH 3.0 Mechanism (Pressure
& Temperature dependent Reactions are listed)
Sr.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41

Reactions
O+H2<=>H+OH
O+H2O2<=>OH+HO2
O+CH4<=>OH+CH3
O+CH3OH<=>OH+CH2OH
O+CH3OH<=>OH+CH3O
O+C2H2<=>H+HCCO
O+C2H2<=>OH+C2H
O+C2H2<=>CO+CH2
O+C2H4<=>CH3+HCO
O+C2H6<=>OH+C2H5
H+O2<=>O+OH
H+H2O2<=>HO2+H2
H+CH3(+M)<=>CH4(+M)
H+CH4<=>CH3+H2
H+HCO(+M)<=>CH2O(+M)
H+CH2O(+M)<=>CH2OH(+M)
H+CH2O(+M)<=>CH3O(+M)
H+CH2O<=>HCO+H2
H+CH2OH(+M)<=>CH3OH(+M)
H+CH2OH<=>OH+CH3
H+CH2OH<=>CH2(S)+H2O
H+CH3O(+M)<=>CH3OH(+M)
H+CH3O<=>H+CH2OH
H+CH3O<=>OH+CH3
H+CH3O<=>CH2(S)+H2O
H+CH3OH<=>CH2OH+H2
H+CH3OH<=>CH3O+H2
H+C2H3(+M)<=>C2H4(+M)
H+C2H4(+M)<=>C2H5(+M)
H+C2H4<=>C2H3+H2
H+C2H5(+M)<=>C2H6(+M)
H+C2H6<=>C2H5+H2
H2+CO(+M)<=>CH2O(+M)
OH+H2<=>H+H2O
2OH<=>O+H2O
OH+CH3(+M)<=>CH3OH(+M)
OH+CH3<=>CH2+H2O
OH+CH3<=>CH2(S)+H2O
OH+CH4<=>CH3+H2O
OH+CO<=>H+CO2
CH3+CH2O<=>HCO+CH4

(k = A T exp(-E/RT))
A (mole-cmE

sec-K)
(cal/mole)
3.87E+04
2.7
6260
9.63E+06
2
4000
1.02E+09
1.5
8600
3.88E+05
2.5
3100
1.30E+05
2.5
5000
1.35E+07
2
1900
4.60E+19
-1.4
28950
6.94E+06
2
1900
1.25E+07
1.8
220
8.98E+07
1.9
5690
2.65E+16
-0.7
17041
1.21E+07
2
5200
1.39E+16
-0.5
536
6.60E+08
1.6
10840
1.09E+12
0.5
-260
5.40E+11
0.5
3600
5.40E+11
0.5
2600
5.74E+07
1.9
2742
1.06E+12
0.5
86
1.65E+11
0.7
-284
3.28E+13
-0.1
610
2.43E+12
0.5
50
4.15E+07
1.6
1924
1.50E+12
0.5
-110
2.62E+14
-0.2
1070
1.70E+07
2.1
4870
4.20E+06
2.1
4870
6.08E+12
0.3
280
5.40E+11
0.5
1820
1.32E+06
2.5
12240
5.21E+17
-1
1580
1.15E+08
1.9
7530
4.30E+07
1.5
79600
2.16E+08
1.5
3430
3.57E+04
2.4
-2110
2.79E+18
-1.4
1330
5.60E+07
1.6
5420
6.44E+17
-1.3
1417
1.00E+08
1.6
3120
4.76E+07
1.2
70
3.32E+03
2.8
5860
189

42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86

CH3+CH3OH<=>CH2OH+CH4
CH3+CH3OH<=>CH3O+CH4
CH3+C2H4<=>C2H3+CH4
CH3+C2H6<=>C2H5+CH4
HCO+H2O<=>H+CO+H2O
HCO+M<=>H+CO+M
CH3O+O2<=>HO2+CH2O
C2H+H2<=>H+C2H2
C2H3+O2<=>HCO+CH2O
C2H4(+M)<=>H2+C2H2(+M)
N+O2<=>NO+O
NH+O2<=>NO+OH
NH2+OH<=>NH+H2O
NNH+M<=>N2+H+M
H+NO+M<=>HNO+M
HNO+H<=>H2+NO
HNO+OH<=>NO+H2O
CN+H2<=>HCN+H
NCO+NO<=>N2O+CO
NCO+NO<=>N2+CO2
HCN+M<=>H+CN+M
HCN+O<=>NCO+H
HCN+O<=>NH+CO
HCN+O<=>CN+OH
HCN+OH<=>HOCN+H
HCN+OH<=>HNCO+H
HCN+OH<=>NH2+CO
CH+N2<=>HCN+N
CH2+NO<=>H+HNCO
CH2+NO<=>OH+HCN
CH2+NO<=>H+HCNO
CH2(S)+NO<=>H+HNCO
CH2(S)+NO<=>OH+HCN
CH2(S)+NO<=>H+HCNO
HNCO+O<=>NH+CO2
HNCO+O<=>HNO+CO
HNCO+O<=>NCO+OH
HNCO+H<=>NH2+CO
HNCO+H<=>H2+NCO
HNCO+OH<=>NCO+H2O
HNCO+OH<=>NH2+CO2
HCNO+H<=>H+HNCO
HCNO+H<=>OH+HCN
HCNO+H<=>NH2+CO
HOCN+H<=>H+HNCO

3.00E+07
1.00E+07
2.27E+05
6.14E+06
1.50E+18
1.87E+17
4.28E-13
5.68E+10
4.58E+16
8.00E+12
9.00E+09
1.28E+06
9.00E+07
1.30E+14
4.48E+19
9.00E+11
1.30E+07
2.95E+05
1.90E+17
3.80E+18
1.04E+29
2.03E+04
5.07E+03
3.91E+09
1.10E+06
4.40E+03
1.60E+02
3.12E+09
3.10E+17
2.90E+14
3.80E+13
3.10E+17
2.90E+14
3.80E+13
9.80E+07
1.50E+08
2.20E+06
2.25E+07
1.05E+05
3.30E+07
3.30E+06
2.10E+15
2.70E+11
1.70E+14
2.00E+07

1.5
1.5
2
1.7
-1
-1
7.6
0.9
-1.4
0.4
1
1.5
1.5
-0.1
-1.3
0.7
1.9
2.5
-1.5
-2
-3.3
2.6
2.6
1.6
2
2.3
2.6
0.9
-1.4
-0.7
-0.4
-1.4
-0.7
-0.4
1.4
1.6
2.1
1.7
2.5
1.5
1.5
-0.7
0.2
-0.8
2

9940
9940
9200
10450
17000
17000
-3530
1993
1015
86770
6500
100
-460
4980
740
660
-950
2240
740
800
126600
4980
4980
26600
13370
6400
9000
20130
1270
760
580
1270
760
580
8500
44000
11400
3800
13300
3600
3600
2850
2120
2890
2000

190

Sr.
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43

Table 7.4. Some Important Reactions of UBC MECH2.0 Mechanism (only

Pressure & Temperature dependent Reactions are listed)
(k = A T exp(-E/RT))
Reactions
A (mole-cm-sec-K)

E (cal/mole)
O+H2<=>H+OH
5.00E+04
2.7
6290
O+H2O2<=>OH+HO2
9.63E+06
2
4000
O+CH4<=>OH+CH3
1.02E+09
1.5
8600
O+CH3OH<=>OH+CH2OH
3.88E+05
2.5
3100
O+CH3OH<=>OH+CH3O
1.30E+05
2.5
5000
O+C2H2<=>H+HCCO
1.02E+07
2
1900
O+C2H2<=>OH+C2H
4.60E+19
-1.4
28950
O+C2H2<=>CO+CH2
1.02E+07
2
1900
O+C2H4<=>CH3+HCO
1.92E+07
1.8
220
O+C2H6<=>OH+C2H5
8.98E+07
1.9
5690
H+CH3(+M)<=>CH4(+M)
1.27E+16
-0.6
383
H+CH4<=>CH3+H2
6.60E+08
1.6
10840
H+HCO(+M)<=>CH2O(+M)
1.09E+12
0.5
-260
H+CH2O(+M)<=>CH2OH(+M)
5.40E+11
0.5
3600
H+CH2O(+M)<=>CH3O(+M)
5.40E+11
0.5
2600
H+CH2O<=>HCO+H2
2.30E+10
1.1
3275
H+CH3OH<=>CH2OH+H2
1.70E+07
2.1
4870
H+CH3OH<=>CH3O+H2
4.20E+06
2.1
4870
H+C2H3(+M)<=>C2H4(+M)
6.08E+12
0.3
280
H+C2H4(+M)<=>C2H5(+M)
1.08E+12
0.5
1820
H+C2H4<=>C2H3+H2
1.32E+06
2.5
12240
H+C2H5(+M)<=>C2H6(+M)
5.21E+17
-1
1580
H+C2H6<=>C2H5+H2
1.15E+08
1.9
7530
OH+H2<=>H+H2O
2.16E+08
1.5
3430
OH+CH2<=>CH+H2O
1.13E+07
2
3000
OH+CH3<=>CH2+H2O
5.60E+07
1.6
5420
OH+CH4<=>CH3+H2O
1.00E+08
1.6
3120
OH+CO<=>H+CO2
4.76E+07
1.2
70
OH+CH2O<=>HCO+H2O
3.43E+09
1.2
-447
OH+CH3OH<=>CH2OH+H2O
1.44E+06
2
-840
OH+CH3OH<=>CH3O+H2O
6.30E+06
2
1500
OH+C2H2<=>H+CH2CO
2.18E-04
4.5
-1000
OH+C2H2<=>H+HCCOH
5.04E+05
2.3
13500
OH+C2H2<=>C2H+H2O
3.37E+07
2
14000
OH+C2H2<=>CH3+CO
4.83E-04
4
-2000
OH+C2H4<=>C2H3+H2O
3.60E+06
2
2500
OH+C2H6<=>C2H5+H2O
3.54E+06
2.1
870
CH+H2<=>H+CH2
1.11E+08
1.8
1670
CH2+H2<=>H+CH3
5.00E+05
2
7230
CH2+CH4<=>2CH3
2.46E+06
2
8270
CH2+CO(+M)<=>CH2CO(+M)
8.10E+11
0.5
4510
2CH3(+M)<=>C2H6(+M)
2.12E+16
-1
620
2CH3<=>H+C2H5
4.99E+12
0.1
10600
191

44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

CH3+CH2O<=>HCO+CH4
CH3+CH3OH<=>CH2OH+CH4
CH3+CH3OH<=>CH3O+CH4
CH3+C2H4<=>C2H3+CH4
CH3+C2H6<=>C2H5+CH4
HCO+H2O<=>H+CO+H2O
HCO+M<=>H+CO+M
CH3O+O2<=>HO2+CH2O
C2H+H2<=>H+C2H2
C2H4(+M)<=>H2+C2H2(+M)
CH3+O2<=>CH3O2
C2H5+O2<=>C2H5O2
C2H5+O2<=>C2H5O+O
C2H5+O2<=>CH3CHO+OH
C2H3+O2<=>C2H3O+O
C2H3+O2<=>C2H2+HO2
OH+C3H8<=>C3H7+H2O

3.32E+03
3.00E+07
1.00E+07
2.27E+05
6.14E+06
2.24E+18
1.87E+17
4.28E-13
4.07E+05
8.00E+12
8.52E+58
1.10E+47
1.10E+13
1.60E+14
6.61E+06
8.40E+05
7.08E+06

2.8
1.5
1.5
2
1.7
-1
-1
7.6
2.4
0.4
-15
-10.6
-0.2
-1.2
1.9
1.9
1.9

5860
9940
9940
9200
10450
17000
17000
-3530
200
88770
17018
14830
27926
10392
979
2246
158.9

Table 7.2 shows some common species and intermediates (or radicals) present in the
reacting mixture for both detailed kinetic models and these models have about 44 common
reactions. In Table 7.3 & 7.4, only the pressure dependent reactions are listed as apparent
from value of Arrhenius parameter .
We have simulated the combustion of methane with four models (Table 7.1) with different
engine specifications (An example of engine specifications is given in Table 7.5).

Table 7.5 Example of Test Engines Specifications used in Simulation of Methane

Combustion
Parameters
Values
Compression Ratio

10.0

Cylinder clearance volume (cm3)

1530

Engine Speed (rpm)

1000

Connecting rod to crank radius ratio

Cylinder bore diameter (mm)

2.97729
102

Displacement (cm)
More details about the engine specifications, used in this simulation, exist in the literature.
The other simulation inputs to the CHEMKIN software are given in Table7.6 and adopted
from Heywood.
192

Table 7.6 General Input Parameters;

Parameters
Heat transfer correlation coefficients

Woschni Correlation coefficients

Values
Coefficient a

0.035

Coefficient b
Coefficient c

0.71
0.0

C11

2.28

C12
C2

0.308
3.24

Wall Temperature (K)

400

The composition of the initial gas mixture is a combination of natural gas, air, and Exhaust
Gas Recirculation (EGR) gas and is given in Table 7.7.

Table 7.7 Composition (Mole Fraction) of Initial Gas Mixture

Species
CH4
C2H6
C3H8
CO2
N2

7.3

Mole Fraction
0.8709
0.105
0.0027
0.0205
0.072

Results & Discussion:

The combustion of methane in engine cylinder was simulated with four kinetic

model schemes and we used various input parameters.

In this section, we focus more on the consequences of the used four kinetic reaction
schemes (models) methane oxidation for the predicted pressure, temperature, profiles and
major combustion species including gaseous pollutants. The predicting capabilities of
theses models under similar simulation conditions were also discussed and an appropriate
reaction scheme (detailed & reduced) was identified simply based on the simulation results.
Figure 7.1 &7.2 shows the pressure and temperature profiles respectively of four
models for the adiabatic and stoichiometric conditions (Initial Inlet Temperature, Tini=447
K, Initial Inlet Pressure, Pini=1.07 bar and =1.0). As shown in the figures, reduced model
193

(Duterque, Jones and Lindstedt) predict the earlier combustion that with the detailed
models. The reason of this deviation in delay is that the species and temperature reaches
their end values very sharply. Each pressure profile clearly show that the peak cylinder
pressure occur close to TC (Top-Center). At TC, this pressure built up is closely related to
the rate of burning of the premixed fuel mixture. There is early built up of pressure with
reduced model (Duterque, Jones and Lindstedt) than detailed reaction schemes (UBC
MECH2.0 & GRIMECH 3.0). The detailed models predict the maximum cylinder pressure
and temperature of approximately of 40 atm and 2000 K respectively. In case of reduced
models, the predicted pressure and temperature significantly deviate.

Figure 7.1 Predicted Pressure Profiles for Equivalence Ratio of =1.0 (Tini=447 K,
Pini=1.07 bar)
These deviations prediction of pressure and temperature occur due to reaction paths for of
detailed and reduced models.

194

Figure 7.2 Predicted Temperature Profiles for Equivalence Ratio of =1.0

(Tini=447 K, Pini=1.07 bar)
Figure 7.3 demonstrate the main combustion species profiles of fuel (CH4, CO2), and water
vapours (H2O) at stoichiometric conditions. Obviously, 4-step model predicts the early
consumption of fuel than the both detailed models. If we look at the profiles of the
produced species (CO2 and H2O), 4-step model dictate that these species are formed at the
earlier stage very rapidly and later on, these consumed at the intermediates steps (which
indicate the pyrolysis of fuel) and then produced. These intermediates then further oxidized
to CO which then oxidized to CO2.

195

196

Figure 7.3 Major Species Profiles for Equivalence Ratio of =1.0 (Tini=447 K,
Pini=1.07 bar).
It is clear from Figure 7.3 that, both detailed models (GRIMECH 3.0 & UBC MECH2.0)
and 4-steps model predict CO emissions and one step global model fails in this regard
because there is no CO pathway in the model. In each graph of CO and NOx (as NO2),
reduced model show the early formation than detailed models.

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Figure 7.4 NOx and CO Emissions for Equivalence Ratio of =1.0 (Tini=447 K,
Pini=1.07 bar). [Note; NOx is used as collective term for NO2 & N2O]
Each profile of N2O graph illustrate that N2O is formed immediately during the combustion
and then its fraction decreased as shown in Figure 7.4. The reason for this production of
N2O production is oxidation N2 with O2 and the further conversion into NO2 and NO. There
is rapid formation of NO than NO2. On the whole, reduced models (only the 4-steps
mechanism) predict the higher fractions than the detailed reaction schemes.
In the light of above simulation results, detailed models are more appropriate in prediction
of combustion species and pollutants formation in IC engine chamber. The results (Figure
5.1-5.4) of present study predict that GRIMECH3.0 model could be utilized in practical
design on an IC engine for low emissions.

7.4

Summary:
In this chapter, combustion of methane (major constituent of natural gas or CNG,

about 90% by wt) was simulated using four kinetic models of methane in CHEMKIN 4.1.1
for 0-D closed internal combustion (IC) engine reactor. Two detailed (GRIMECH3.0 &
UBC MECH2.0) and two reduced (One step & 4-step) models were examined for various
IC engine designs. The detailed models (GRIMECH3.0, & UBC MECH2.0) and 4-step
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models successfully predicted the combustion while global model unable to predict any
combustion reaction. This study illustrated that the detailed model showed good
concordances in the prediction of chamber pressure, temperature and major combustion
species profiles. The detailed models also exhibited the capabilities to predict the pollutants
formation in an IC engine while reduced schemes showed failure in the prediction of
pollutants emissions.

Although, there are discrepancies among the profiles of four

considered model, the detailed models (GRIMECH3.0 & UBC MECH2.0) produced the
acceptable agreement in the species prediction and formation of pollutants.

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