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Journal of Natural Gas Chemistry 19(2010)

Kinetic models of natural gas combustion in an


internal combustion engine
M. Mansha1 ,

A. R Saleemi1 ,

Badar M. Ghauri2

1. Department of Chemical Engineering, University of Engineering & Technology Lahore-Pakistan 54570;


2. SUPARCO, HQs, Karachi, Pakistan -49430
[ Received May 9, 2009; Revised June 4, 2009; Available online December 24, 2009 ]

Abstract
In this study, 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 4-step models successfully predicted the combustion
while global model was 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 the 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.
Key words
kinetic models; detailed models; reduced models; combustion; methane; IC engine

1. Introduction
The combustion of hydrocarbon fuel removes O2 from
the atmosphere and releases equivalent amount of H2 O and
CO2 inevitably mingled with trace amounts of numerous
other compounds including hydrocarbons (CH4 , C2 H2 , C6 H6 ,
CH2 , CHO, etc.), carbon monoxide (CO), nitrogen oxides
(NO, N2 O) and reduced nitrogen (NH3 and HCN), sulfur
gases (SO2 , OCS, CS2 ), halo-carbons (CHCI and CH3 Br),
and particles [1].
Heywood [2] described that in light duty 4-stroke engine,
a premixed fuel-air mixture (CNG-Air) enters the engine during the intake stroke, which starts when the piston is at top
center (TC) and ends with the piston at bottom center (BC),
and draws fresh mixture into the cylinder. To increase the
mass inducted, the inlet valve opens shortly before the intake
stroke starts and closes after it ends. The mixture is compressed to small fraction of its volume in the compression
stroke. Towards the end of the compression stroke, combustion is initiated by the spark plug typically. As the combustion progresses, the cylinder pressure rises more rapidly when
both intake and exhaust valves are closed. The power stroke,
or expansion stroke starts with the piston at TC and ends at

BC as high temperature and high pressure gases push the piston down and force the crank to rotate. During an exhaust
stroke, the remaining burned gases exit the cylinder; first because the cylinder pressure may be substantially higher than
the exhaust pressure; then as they are swept out by the piston
as it moves towards TC. When the piston approaches the TC,
the inlet valve opens. Just after TC, the exhaust valve closes
and the cycle starts again. An illustrative example of possible
trend of measured cylinder pressure is given in Figure 1.
Because of the unique tetrahedral molecular structure
with large CH bond energies, methane exhibits some unique
combustion characteristics. For example it has high ignition
temperature, low flame speed and it is essentially unreactive in
photochemical smog chemistry. Chemical kinetics of methane
is the most widely studied topic. Kaufman [6], in a review
of combustion kinetics indicated that the methane combustion
models evolved in the period of 19701982 from less than
15 elementary steps with 12 species to 75 elementary steps,
plus the 75 reverse reactions, with 25 species. Recently, several research groups have collaborated in the creation of an
optimized methane kinetic model [7]. This mechanism designated GRI MECH3.0 is based on the optimization techniques
of Frenklach et al. [8]. Various detailed reaction models are

Corresponding author. Tel: +92-333-4847327; E-mail: muhammad mansha@uet.edu.pk

Copyright2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(08)60150-4

M. Mansha et al./ Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

reported in the literature [9]. They can be divided into full


models, skeletal models, and reduced models. These models differ with respect to the considered species and reactions
[10]. In literature, several models of methane combustion exist. For example:
Detailed models include those of Westbrook [11], Glarborg et al. [12], Miller and Bowman [13], Konnov [14],
Hughes et al. [15], and the standard GRI MECH3.0 [16].
Reduced models include Westbrook and Dryer [17],
Duterque et al. [18] (1 to 2 global reactions), Peters [19],
Hautman et al., [20], Jones and Lindstedt [21] (more than
2 global reaction), Edelman and Fortune [22], and Edelman
and Harsha [23]-one step global reaction with many elementary reactions; (these models are called quasi-global models).
All chemical models used in combustion share the same description of elementary chemical reactions, based on an Arrhenius law, leading to a rate coefficient expressed as k =
AT eE a /RT . The values of A, E a (or T a = Ea /R) and the
temperature-dependent coefficient are thus reaction dependent. Based on this expression, different levels of approximation can be defined to describe the kinetics.

Figure 1. Measured cylinder pressure for ten cycles in single cylinder SI engine operating at 1500 rpm, = 1.0, Pin = 0.7 atm (Taken from Heywood [2])

Oxidation models of methane combustion, reported in


the literatures [625], 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 from 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
H2 O etc. in engine combustion chamber is identified. The
simple criteria of comparing simulation results (profiles) of
detailed and reduced models as followed in the study was described in Ref[26].
2. Materials and methods
CHEMKIN is a powerful set of software tools for solving complex chemical kinetics problems. It is used to study
reacting flows, such as those found in combustion, catalysis,
chemical vapour deposition, and plasma etching. CHEMKIN
consists of rigorous gas-phase and gas-surface chemical kinetics in a variety of reactor models that can be used to represent the specific set of systems of interest. It provides a
broad capability that addresses needs of both non-expert and
expert users [27]. The IC model is for 0-D closed system,
the simulation is only valid within the time period when both
intake and exhaust valves are closed. Conventionally, engine
cylinder events are expressed in crank rotation angle relative
to the top dead center (TDC). The intake valve close (IVC)
time of our test engine is 142 degrees (crank angle) before
TDC (BTDC).
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. The following four mechanisms were investigated for methane combustion in internal combustion engines as given in Table 1.

Table 1. Tested models of methane combustion


Sr. No
1
2

3
4

Kinetic model type

Reactions

Global one-step reaction [18]


Four step reaction models of Jones and Lindstedt [21]

Arrhenius parameters
A

T a (K)
1.50E+13
0.0
20000.0
4.40E+14
0.0
24000.0
3.00E+1
0.0
24000.0
2.50E+1
1.0
32000.0
2.75E+12
0.0
16000.0

CH4 +2O=CO2 +2H2 O


(i) CH4 +1/2O2 = CO+2H2
(ii) CH4 +H2 O = CO+3H2
(iii) H2 +1/2O2 = H2 O
(iv) CO+H2 O = CO2 +H2
GRIMECH 3.0 (53 species & 325 reactions) (available on Internet) [7]
UBC MECH2.0 Kinetic mechanism available on Internet at http://kbspc.mech.ubc.ca/kinetics.html

Where, A, , T a (Ta = Ea /T ) are the parameters for ArEa


rhenius Law defined below: k = AT e RT . Two of these
model are the detailed such as GRIMECH 3.0 & UBC
MECH2.0 and other two are reduced such as Duterque

(Global One Step)


Two types of data
tion of CHEMKIN
(ii) thermodynamic

& Jones and Lindstedt (Four Steps).


files are required to input for execumodule; (i) Mechanism data files and
data files. The details of mechanism

Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

and thermodynamics files can be found in references at


[7,18,28]. Some important species and reaction (pressure

dependent) of both detailed models are given in Table 2 to


Table 4.

Table 2. Important species considered in UBC MECH 2.0 and GRI MECH 3.0 kinetic models
Detailed kinetic model
UBC MECH2.0

No. of species
54

No. of reactions
277

GRI3.0

53

325

Important reacting species/intermediates (radicals)


H2 , H, O, O2 , OH, H2 O, HO2 , H2 O2 , C, CH, CH2 , CH2 (S), CH3 , CH4 , CO2 ,
CO, CH2 O, CH2 OH, CH3 O, CH3 OH, C2 H, C2 H2 , C2 H3 , C2 H4 , C2 H5 , C2 H6 ,
HCCO, CH2 CO, HCCOH, N2 , AR, CH3 O2 , CH3 O2 H, C2 H5 O, C2 H5 O2 , C2 H5 O2 H,
CH3 CO, CH3 CHO, C2 H4 O, C2 H3 O, C3 H8 , nC3 H7 , iC3 H7 , nC3 H7 O2 , iC3 H7 O2 ,
nC3 H7 O2 H, iC3 H7 O2 H, nC3 H7 O, iC3 H7 O, C3 H6 , C3 H5 , C3 H4 , C2 H4 O2 H
O, O2 , OH, H2 O, HO2 , H2 O2 , C, CH, CH2 , CH2 (S), CH3 , CH4 , CO, CO2 , HCO,
CH2 O, CH2 OH, CH3 O, CH3 OH, C2 H, C2 H2 , C2 H3 , C2 H4 , C2 H5 , C2 H6 , HCCO,
CH2 CO, HCCOH, N, NH, NH2 , NH3 , NNH, NO, NO2 , N2 O, HNO, CN, HCN, H2 CN,
HCNN, HCNO, HOCN, HNCO, NCO, N2 , AR, C3 H7 , C3 H8 , CH2 CHO

Table 3. Some important reactions of GRI MECH 3.0 mechanism (pressure & temperature dependent reactions are listed)
Sr. No

Reactions

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
44
45
46
47

O+H2 H+OH
O+H2 O2 OH+HO2
O+CH4 OH+CH3
O+CH3 OH OH+CH2 OH
O+CH3 OH OH+CH3 O
O+C2 H2 H+HCCO
O+C2 H2 OH+C2 H
O+C2 H2 CO+CH2
O+C2 H4 CH3 +HCO
O+C2 H6 OH+C2 H5
H+O2 O+OH
H+H2 O2 HO2 +H2
H+CH3 (+M) CH4 (+M)
H+CH4 CH3 +H2
H+HCO(+M) CH2 O(+M)
H+CH2 O(+M) CH2 OH(+M)
H+CH2 O(+M) CH3 O(+M)
H+CH2 O HCO+H2
H+CH2 OH(+M) CH3 OH(+M)
H+CH2 OH OH+CH3
H+CH2 OH CH2 (S)+H2 O
H+CH3 O(+M) CH3 OH(+M)
H+CH3 O H+CH2 OH
H+CH3 O OH+CH3
H+CH3 O CH2 (S)+H2 O
H+CH3 OH CH2 OH+H2
H+CH3 OH CH3 O+H2
H+C2 H3 (+M) C2 H4 (+M)
H+C2 H4 (+M) C2 H5 (+M)
H+C2 H4 C2 H3 +H2
H+C2 H5 (+M) C2 H6 (+M)
H+C2 H6 C2 H5 +H2
H2 +CO(+M) CH2 O(+M)
OH+H2 H+H2 O
2OH O+H2 O
OH+CH3 (+M) CH3 OH(+M)
OH+CH3 CH2 +H2 O
OH+CH3 CH2 (S)+H2 O
OH+CH4 CH3 +H2 O
OH+CO H+CO2
CH3 +CH2 O HCO+CH4
CH3 +CH3 OH CH2 OH+CH4
CH3 +CH3 OH CH3 O+CH4
CH3 +C2 H4 C2 H3 +CH4
CH3 +C2 H6 C2 H5 +CH4
HCO+H2 O H+CO+H2 O
HCO+M H+CO+M

k = A T exp(E/RT )
A (molcmsecK)

3.87E+04
2.7
9.63E+06
2.0
1.02E+09
1.5
3.88E+05
2.5
1.30E+05
2.5
1.35E+07
2.0
4.60E+19
1.4
6.94E+06
2.0
1.25E+07
1.8
8.98E+07
1.9
2.65E+16
0.7
1.21E+07
2.0
1.39E+16
0.5
6.60E+08
1.6
1.09E+12
0.5
5.40E+11
0.5
5.40E+11
0.5
5.74E+07
1.9
1.06E+12
0.5
1.65E+11
0.7
3.28E+13
0.1
2.43E+12
0.5
4.15E+07
1.6
1.50E+12
0.5
2.62E+14
0.2
1.70E+07
2.1
4.20E+06
2.1
6.08E+12
0.3
5.40E+11
0.5
1.32E+06
2.5
5.21E+17
1.0
1.15E+08
1.9
4.30E+07
1.5
2.16E+08
1.5
3.57E+04
2.4
2.79E+18
1.4
5.60E+07
1.6
6.44E+17
1.3
1.00E+08
1.6
4.76E+07
1.2
3.32E+03
2.8
3.00E+07
1.5
1.00E+07
1.5
2.27E+05
2.0
6.14E+06
1.7
1.50E+18
1.0
1.87E+17
1.0

E (cal/mol)
6260
4000
8600
3100
5000
1900
28950
1900
220
5690
17041
5200
536
10840
260
3600
2600
2742
86
284
610
50
1924
110
1070
4870
4870
280
1820
12240
1580
7530
79600
3430
2110
1330
5420
1417
3120
70
5860
9940
9940
9200
10450
17000
17000

M. Mansha et al./ Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

Sr. No

Reactions

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 O+O2 HO2 +CH2 O


C2 H+H2 H+C2 H2
C2 H3 +O2 HCO+CH2 O
C2 H4 (+M) H2 +C2 H2 (+M)
N+O2 NO+O
NH+O2 NO+OH
NH2 +OH NH+H2 O
NNH+M N2 +H+M
H+NO+M HNO+M
HNO+H H2 +NO
HNO+OH NO+H2 O
CN+H2 HCN+H
NCO+NO N2 O+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+H2 O
HNCO+OH NH2 +CO2
HCNO+H H+HNCO
HCNO+H OH+HCN
HCNO+H NH2 +CO
HOCN+H H+HNCO

Table 3. Continue
k = A T exp(E/RT )
A (molcmsecK)

4.28E-13
7.6
5.68E+10
0.9
4.58E+16
1.4
8.00E+12
0.4
9.00E+09
1.0
1.28E+06
1.5
9.00E+07
1.5
1.30E+14
0.1
4.48E+19
1.3
9.00E+11
0.7
1.30E+07
1.9
2.95E+05
2.5
1.90E+17
1.5
3.80E+18
2.0
1.04E+29
3.3
2.03E+04
2.6
5.07E+03
2.6
3.91E+09
1.6
1.10E+06
2.0
4.40E+03
2.3
1.60E+02
2.6
3.12E+09
0.9
3.10E+17
1.4
2.90E+14
0.7
3.80E+13
0.4
3.10E+17
1.4
2.90E+14
0.7
3.80E+13
0.4
9.80E+07
1.4
1.50E+08
1.6
2.20E+06
2.1
2.25E+07
1.7
1.05E+05
2.5
3.30E+07
1.5
3.30E+06
1.5
2.10E+15
0.7
2.70E+11
0.2
1.70E+14
0.8
2.00E+07
2.0

E (cal/mol)
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

Table 4. Some important reactions of UBC MECH2.0 mechanism (only pressure & temperature dependent reactions are listed)
Sr. No

Reactions

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

O+H2 H+OH
O+H2 O2 OH+HO2
O+CH4 OH+CH3
O+CH3 OH OH+CH2 OH
O+CH3 OH OH+CH3 O
O+C2 H2 H+HCCO
O+C2 H2 OH+C2 H
O+C2 H2 CO+CH2
O+C2 H4 CH3 +HCO
O+C2 H6 OH+C2 H5
H+CH3 (+M) CH4 (+M)
H+CH4 CH3 +H2
H+HCO(+M) CH2 O(+M)
H+CH2 O(+M) CH2 OH(+M)
H+CH2 O(+M) CH3 O(+M)
H+CH2 O HCO+H2
H+CH3 OH CH2 OH+H2
H+CH3 OH CH3 O+H2
H+C2 H3 (+M) C2 H4 (+M)
H+C2 H4 (+M) C2 H5 (+M)

A(molcmsecK)
5.00E+04
9.63E+06
1.02E+09
3.88E+05
1.30E+05
1.02E+07
4.60E+19
1.02E+07
1.92E+07
8.98E+07
1.27E+16
6.60E+08
1.09E+12
5.40E+11
5.40E+11
2.30E+10
1.70E+07
4.20E+06
6.08E+12
1.08E+12

k = A T exp(E/RT )

2.7
2.0
1.5
2.5
2.5
2.0
1.4
2.0
1.8
1.9
0.6
1.6
0.5
0.5
0.5
1.1
2.1
2.1
0.3
0.5

E (cal/mol)
6290
4000
8600
3100
5000
1900
28950
1900
220
5690
383
10840
260
3600
2600
3275
4870
4870
280
1820

Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

Table 4. Continue
Sr. No

Reactions

21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

H+C2 H4 C2 H3 +H2
H+C2 H5 (+M) C2 H6 (+M)
H+C2 H6 C2 H5 +H2
OH+H2 H+H2 O
OH+CH2 CH+H2 O
OH+CH3 CH2 +H2 O
OH+CH4 CH3 +H2 O
OH+CO H+CO2
OH+CH2 O HCO+H2 O
OH+CH3 OH CH2 OH+H2 O
OH+CH3 OH CH3 O+H2 O
OH+C2 H2 H+CH2 CO
OH+C2 H2 H+HCCOH
OH+C2 H2 C2 H+H2 O
OH+C2 H2 CH3 +CO
OH+C2 H4 C2 H3 +H2 O
OH+C2 H6 C2 H5 +H2 O
CH+H2 H+CH2
CH2 +H2 H+CH3
CH2 +CH4 2CH3
CH2 +CO(+M) CH2 CO(+M)
2CH3 (+M) C2 H6 (+M)
2CH3 H+C2 H5
CH3 +CH2 O HCO+CH4
CH3 +CH3 OH CH2 OH+CH4
CH3 +CH3 OH CH3 O+CH4
CH3 +C2 H4 C2 H3 +CH4
CH3 +C2 H6 C2 H5 +CH4
HCO+H2 O H+CO+H2 O
HCO+M H+CO+M
CH3 O+O2 HO2 +CH2 O
C2 H+H2 H+C2 H2
C2 H4 (+M) H2 +C2 H2 (+M)
CH3 +O2 CH3 O2
C2 H5 +O2 C2 H5 O2
C2 H5 +O2 C2 H5 O+O
C2 H5 +O2 CH3 CHO+OH
C2 H3 +O2 C2 H3 O+O
C2 H3 +O2 C2 H2 +HO2
OH+C3 H8 iC3 H7 +H2 O

A(molcmsecK)
1.32E+06
5.21E+17
1.15E+08
2.16E+08
1.13E+07
5.60E+07
1.00E+08
4.76E+07
3.43E+09
1.44E+06
6.30E+06
2.18E-04
5.04E+05
3.37E+07
4.83E-04
3.60E+06
3.54E+06
1.11E+08
5.00E+05
2.46E+06
8.10E+11
2.12E+16
4.99E+12
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

Table 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 3 & 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 1) with different engine specifications (An example of engine specifications is given in Table 5).
More details about the engine specifications, used in this
simulation, exist in studies cited at References [5,27,29]. The
other simulation inputs to the CHEMKIN software are given
in Table 6 and adopted from Heywood [2].
Table 5. Example of test engines specifications used in
simulation of methane combustion
Parameters
Compression ratio
Cylinder clearance volume (cm3 )
Engine speed (rpm)
Connecting rod to crank radius ratio
Cylinder bore diameter (mm)
Displacement (cm)

Values
10.0
1530
1000
2.97729
102

k = A T exp(E/RT )

2.5
1.0
1.9
1.5
2.0
1.6
1.6
1.2
1.2
2.0
2.0
4.5
2.3
2.0
4.0
2.0
2.1
1.8
2.0
2.0
0.5
1.0
0.1
2.8
1.5
1.5
2.0
1.7
1.0
1.0
7.6
2.4
0.4
15.0
10.6
0.2
1.2
1.9
1.9
1.9

E (cal/mol)
12240
1580
7530
3430
3000
5420
3120
70
447
840
1500
1000
13500
14000
2000
2500
870
1670
7230
8270
4510
620
10600
5860
9940
9940
9200
10450
17000
17000
3530
200
88770
17018
14830
27926
10392
979
2246
158.9

Table 6. General input parameters


Parameters
Heat transfer correlation coefficients

Woschni correlation coefficients

Coefficient a
Coefficient b
Coefficient c
C11
C12
C2

Wall temperature (K)

Values
0.035
0.71
0.0
2.28
0.308
3.24
400

The composition of the initial gas mixture is a combination of natural gas, air, and exhaust gas recirculation (EGR)
gas as given in Table 7.
Table 7. Composition (mole fraction) of initial gas mixture
Species
CH4
C2 H6
C3 H8
CO2
N2

Mole fraction
0.8709
0.105
0.0027
0.0205
0.072

M. Mansha et al./ Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

3. Results and 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) of methane oxidation for the predicted pressure, temperature profiles and major combustion species including gaseous pollutants. The predicting capabilities of theses models under the similar simulation conditions were also discussed and an appropriate reaction scheme (detailed & reduced) was identified simply based
on the simulation results.
Figure 2 &3 shows the pressure and temperature profiles
respectively of four models for the adiabatic and stoichiomet-

ric conditions (Initial inlet temperature, Tini = 447 K, initial


inlet pressure, Pini = 1.07 bar and = 1.0). As shown in the
Figures, the reduced model (Duterque, Jones and Lindstedt)
predicts the earlier combustion as the detailed models. The
reason of this deviation in delay is that the species and temperature reache their end values very sharply. Each pressure
profile clearly shows that the peak cylinder pressure occurs
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 an early built up of pressure with the reduced
model (Duterque, Jones and Lindstedt) than the 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 2. Predicted pressure profiles for equivalence ratio of = 1.0 (Tini = 447 K, Pini = 1.07 bar)

Figure 3. Predicted temperature profiles for equivalence ratio of = 1.0 (Tini = 447 K, Pini = 1.07 bar)

These deviations in the prediction of pressure and temperature occur due to reaction paths for the detailed and reduced
models.

Figure 4 demonstrates the main combustion species


profiles of fuel (methane, CH4 ), carbon dioxide (CO2 ), and
water vapours (H2 O) at stoichiometric conditions. Obviously,

Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

the 4-step model better predicts the early consumption of fuel


than both the detailed models. If we look at the profiles of the
produced species (CO2 and H2 O), 4-step model indicates that
these species are formed at the earlier stage very rapidly and
later on, these are consumed at the intermediate steps (which
indicate the pyrolysis of fuel) and then produced. These intermediates then further are oxidized to CO which is then ox-

idized to CO2 .
It is clear from Figure 4 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 ), the reduced model shows the
earlier formation than the detailed models.

Figure 4. Major species profiles (a) CH4 , (b) CO2 , (c) H2 O for equivalence ratio of = 1.0 (Tini = 447 K, Pini = 1.07 bar)

M. Mansha et al./ Journal of Natural Gas Chemistry Vol. 19 No. 1 2010

Each profile of N2 O graph illustrates that N2 O is formed


immediately during the combustion and then its fraction is decreased as shown in Figure 5. The reason for this production
of N2 O production is the oxidation of N2 with O2 and the fur-

ther conversion into NO2 and NO. There is more rapid formation of NO than NO2 on the whole, the reduced models (only
the 4-steps mechanism) predict the higher fractions than the
detailed reaction schemes.

Figure 5. NOx (a) and CO (b) emissions for equivalence ratio of = 1.0 (Tini = 447 K, Pini = 1.07 bar). NOx is used as collective term for NO2 & N2 O

In the light of the above simulation results, detailed models are more appropriate in prediction of combustion species
and pollutants formation in IC engine chamber. The results
(Figures 25) of present study predict that GRIMECH3.0
model could be utilized in practical design on an IC engine
for low emissions.
4. Conclusions
Combustion in an IC engine was simulated using four reaction models (two detailed and two reduced). The effect of
these reaction schemes on the pressure profiles, temperature
profiles and major species profiles was compared under various simulation conditions (equivalence ratios, engine parameters keeping initial gas composition constant). The detailed
models showed the encouraging results but the computational
cost of a simulation is high. The comparison of the predicted
temperature profiles, major species profiles and pollutants

emission for detailed models identified some of the discrepancies but on the whole the detailed models (GRIMECH3.0 &
UBC MECH2.0) can be superseded over the reduced model
(4-steps model of Jones and Lindstedt) in prediction of pollutants emissions of CO & oxides of nitrogen (NO, N2 O &
NO2 ).
Acknowledgements
Authors are thankful to the Higher Education Commission
(HEC) for financial support for this study and Mr. Jamal Gul for
his continuous technical support during simulation experiments for
keeping the system operational.

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