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Energy Procedia 75 (2015) 3048 – 3053

The 7th International Conference on Applied Energy – ICAE2015

The Effect of CO2 Dilution on the Laminar Burning Velocity

of Premixed Methane/Air Flames
Y. L. Chan*, M.M. Zhu, Z.Z. Zhang, P.F. Liu and D.K. Zhang
Centre for Energy (M473), The University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia

Abstract

The effect of CO2 dilution on the laminar flame speed of methane/air mixture was studied by means of
experimentation and kinetic modelling. Experiments were conducted using a flat-flame burner at atmospheric
pressure and 298K over the methane/air equivalence ratio range of 0.8 to 1.4. Kinetic modelling was performed using
Chemkin Pro, with the skeletal version of Le Cong et al’s kinetic mechanisms. It was found that the laminar flame
speeds measured using the flat flame method were accurate, supported and validated by the literature data. The
laminar flame speed of CH4/air decreased with increasing CO2 dilution. The increase in CO2 concentration reduced
the reactants’ concentrations, decreasing the net reaction rate (and thus the flame speed). In addition, CO2 also acts as
a heat sink, causing a drop in the reaction temperature and thus lowering the ability to overcome the activation energy
for reactions to occur. This study contributes to the understandings of the effect of inert gas on the flammability
characteristics of methane.
© 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2015 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or
Peer-review peer-reviewof
under responsibility under responsibility
Applied of ICAE
Energy Innovation Institute

Keywords: Flammability; Flame Speed; Dilution; Methane/Air Mixture; CO2

1. Introduction

Synthetic gas yielded from the biological and thermochemical conversions of biomass and wastes has
emerged to be an attractive alternative fuel for the internal combustion engines for combined heat and
power (CHP) generations. It is crucial to understand the flammability characteristics of synthetic gas as
they affect the fuel burning rates and engine performance.

In general, the flame of combustible gas/air mixtures can only propagate freely within a limited range
of compositions. Mixtures that are either too rich or too lean are not flammable [1, 2]. This defines the

* Corresponding author. Tel.: +61-8-6488-7600; fax: +61-8-6488-7622.

E-mail address: yii.chan@uwa.edu.au

1876-6102 © 2015 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 Applied Energy Innovation Institute
doi:10.1016/j.egypro.2015.07.621
 Y.L. Chan et al. / Energy Procedia 75 (2015) 3048 – 3053 3049

flammability limits of a combustible gas mixture, which are the lean or lower flammability limit (LFL)
and the rich or upper flammability limit (UFL). Laminar flame speed, which is defined as the propagation
speed of an adiabatic planar flame relative to the unburned gas, is an important parameter in combustion;
this is because it not only affects the tendency of a flame to flashback and blow off, but also plays a role
in the stability of the flame in the combustor [3-5]. It also serves as a useful indicator for the reactivity,
diffusivity and exothermicity of a combustible mixture [3, 5-7]. Flame speed depends on factors such as
temperature, pressure, and mixture composition, and is normally lowest at both ends of the flammability
limits while highest when approaching stoichiometry [1].

Synthetic gas consists of mainly H2, CO, CH4 and CO2 and its composition relies largely on the
feedstock and process conditions. The difference in fuel composition will lead to flame speed variation
and this represents a challenge for the design of a versatile CHP system that works efficiently with
synthetic gas of different compositions. The aim of this work was to study the effect of CO2 dilution (0-
15% vol.) on the laminar flame speed of premixed methane/air mixtures, both experimentally and
numerically. The results would have important implications in the optimisation and safety management of
CHP systems used for synthetic gas, particularly biogas, which is yielded from the anaerobic digestion of
bio-wastes and comprises mainly methane and carbon dioxide.

2. Experimental Details

In the present work, the effect of CO2 dilution on the laminar burning velocity of methane/air mixture
was studied with a flat flame burner using the heat flux method [8, 9]. The reaction mixture, which was
made up from separately metered streams of methane, air and CO2 was introduced into the flat flame
burner via a mixer. Upon ignition, a flame was formed and it travelled upstream towards the burner plate.
Cooling water at constant temperature of 298K was run through the burner with the inlet and outlet
temperatures measured using thermocouples.

The heat flux method is based on the measurement of the net heat loss from the flame to the burner.
This was calculated by measuring the difference between the inlet and outlet temperatures of the cooling
water that flowed through the burner. In theory, by varying the flow rate of the gas mixture, it will
eventually reach a point at which the net heat flux is zero (i.e. the outlet temperature of the cooling water
equals to that of the inlet), and the gas velocity calculated from that flow rate will be the adiabatic flame
speed [4]. However, this is virtually impossible to achieve, i.e. the conductive heat transfer from the flame
to the burner plate is unavoidable. In this work, the flow rate of the fuel/air mixtures were varied and the
resulting temperature differences between the water inlet and outlet were measured, in order to calculate
the heat carried away by the cooling water at each flow rate. The flames were considered to reach steady-
state when the outlet temperature of the cooling water remained constant for at least 20 min. From the
plot of flow velocity vs. heat transfer, the best fit line was extrapolated to zero heat transfer with the
intercept being the adiabatic flame speed [9].

In this work, the dilution was expressed as a fraction of the fuel mixture. For instance, 10 percent
dilution with CO2 means that the fuel is a gas mixture consisting of 90% vol. methane and 10% vol. CO2.
The stoichiometric compositions of the methane/air mixture with different levels of CO2 dilution are
summarised in Table 1.
3050 Y.L. Chan et al. / Energy Procedia 75 (2015) 3048 – 3053

Table 1 The stoichiometric compositions of the methane/air mixture with different levels of CO2 dilution

CO2 Dilution (% vol.) CH4 CO2 O2 N2

0% 0.095 n/a 0.190 0.715
10% 0.094 0.011 0.188 0.707
15% 0.093 0.017 0.187 0.703

3. Modelling Details

Chemkin Pro was used to simulate the one-dimensional freely propagating flame, determining the
premixed, laminar flame speed of the methane/carbon dioxide/air mixture at pressure of 0.1MPa and inlet
temperature of 298K. The skeletal model of Le Cong et al, which consists of 18 species and 66 reactions,
was used in the present work. The full mechanism [10, 11] has been validated over a wide range of
operating conditions and was found to perform better than other models in the previous work of the
authors [12, 13], which focused on NOx-sensitised lower alkanes oxidation under fuel-lean conditions.
The skeletal version was also proven to be able to satisfactorily simulate the flame speed profiles of
methane/air and synthetic gas/air mixtures from literature [14].

For the present simulations, adiabatic condition was assumed (i.e. no heat loss) and the temperature
was computed from the energy equation. A mixture-averaged transport model was used. The adaptive
grid parameters, GRAD and CURV, were varied to obtain grid-independent solutions. Final values of 0.2
and 0.5 were used for the GRAD and CURV parameters, respectively, for all the predictions in this work.
It should also be noted that the Soret effect was not considered in this study.

4. Results and Discussion

Figure 1 compares the flame speed profile of methane/air mixture simulated using the skeletal model
of Le Cong et al with the experimental data obtained from this work and literature [4, 15, 16]. As seen
from Figure 1, the experimental results obtained from the present work are close to the values reported in
the literature. The skeletal model is capable of reproducing the experimental trend, performing well in
predicting the flame speed profile as a function of equivalence ratio. It is significant that the 66 reactions
in the skeletal model represent only a small fraction of the total 924 reactions used in the original
mechanism and yet it is capable of producing reasonably close simulation to the experimental data.
 Y.L. Chan et al. / Energy Procedia 75 (2015) 3048 – 3053 3051

Figure 1 Flame speed profile for methane/air mixture at 0.1 MPa and 298K.Symbols represent experimental data and line denotes
modelling result

Figure 2 depicts the effect of CO2 dilution on the flame speed of methane/air mixture. It is shown that
the increase in CO2 concentration decreased the flame speed of the methane/air flame. Such result is
consistent with the findings published in literature [4, 17, 18]. It may be noted that the experimental data
from Zahedi and Yousefi (2014) was also included in Figure 2 for comparison with this work. Once again,
the skeletal model is capable of reproducing the experimental trend, although quantitative agreement is
not always satisfactory.

Figure 2 Effect of CO2 dilution on the flame speed profile of methane/air mixture at 0.1 MPa and 298K. Symbols represent
experimental data obtained from the present work except for *, which is extracted from Zahedi and Yousefi (2014); lines denote
modelling results

For any diluent, the effect of its addition could be either dilution, transport and thermal diffusions,
chemical, or their combinations, as below [4]:
• Dilution effect - In the presence of diluent, the concentrations of the fuel and oxidant are reduced,
leading to a lower net reaction rate and thus the lower flame speed;
• Transport and thermal effects - When a diluent is added, the mass/thermal diffusivities and the specific
heat capacity of the mixture change, affecting the burning velocity;
3052 Y.L. Chan et al. / Energy Procedia 75 (2015) 3048 – 3053

• Kinetic effect – The diluent involves chemically, altering the reaction kinetics and consequently the
burning velocity

Benedetto et al studied the role of CO2 on the flammability of CH4/O2/N2/CO2 mixtures and has found
that the main effect of CO2 was not on the kinetics or diffusive transport fluxes, but largely thermal, i.e.
the presence of CO2 increased the specific heat of the mixture, lowering the flame temperature and
combustion rate. The same conclusion has been reached in another study conducted using
H2/CO/O2/N2/CO2 mixture by the same group, who further noted that the kinetic effect of CO2 was
relevant only when it was present at high concentrations [19]. Hu et al (2014) has attributed the
decreasing trend of flame speed (with increasing CO2 level) to the dilution, transport, thermal and kinetic
effects. It may be noted although Hu et al reported that CO2 affected the kinetics of methane oxidation
while Benedetto et al concluded CO2’s role was mainly thermal, there is no contradiction between the two
studies. This is because in Hu’s work, they tested CH4/O2/CO2 mixture, where the CO2 concentration was
very high (ranging from 65%-75%). Radiation heat transfer has also been reported to have a role in the
reduction of flame speed with CO2 addition; CO2 is an effective absorber and radiator, causing a greater
radiative heat loss from the flame and thus reducing the adiabatic flame temperature and flame speed [20].

5. Conclusions

Experimental and modelling works have been conducted to investigate the effect of CO2 addition on
the laminar flame speed of methane/air mixture. The skeletal model of Le Cong et al was shown to be
capable of reproducing the experimental trend: the flame speed of methane/air flame decreased in the
presence of CO2. When CO2 was added, the fuel (methane) concentration was diluted and the specific
heat of the mixture increased, leading to a lower flame temperature and consequently the lower laminar
burning velocity.

Acknowledgements

Financial support has been received from the Australian Research Council under the ARC Discovery
Project scheme (DP110103699) and the ARC Linkage Project scheme (LP100200135).

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Biography
Yii Leng Chan works at the Centre for Energy, The University of Western Australia. Her
research interests include the chemical kinetics of combustion and related reactions,
flammability of various combustible gas mixtures, the direct conversion of methane to
methanol etc.