International Journal of Hydrogen Energy 32 (2007) 637 – 646

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Laminar burning velocity of hydrogen–methane/air premixed flames

V. Di Sarli a , A. Di Benedetto b,∗
a Dipartimento di Ingegneria Chimica, Università degli Studi di Napoli “Federico II”, P.le Tecchio 80, 80125 Napoli, Italy
b Istituto di Ricerche sulla Combustione, CNR, Via Diocleziano 328, 80124 Napoli, Italy

Received 9 January 2006; received in revised form 19 May 2006; accepted 30 May 2006
Available online 24 July 2006

Abstract
The laminar burning velocities of hydrogen–methane/air mixtures at NTP conditions were calculated using the CHEMKIN PREMIX code
with the GRI kinetic mechanism. The equivalence ratio and the fuel composition were varied from lean to rich and from pure methane to pure
hydrogen, respectively.
The results show that the values of the blends laminar burning velocities are always smaller than those obtained by averaging the laminar
burning velocities of the pure fuels according to their molar proportions. Moreover, in lean mixtures the hydrogen addition enhances the methane
reactivity slightly, while a strong inhibiting effect of the hydrogen substitution by methane is observed at rich conditions. These findings are
attributed to changes of both, the H radicals concentration and the reactions involving such atoms.
It was attempted to correlate the calculated laminar burning velocities by means of a Le Chatelier’s Rule-like formula. A good prediction
is obtained, except for rich mixtures with high hydrogen contents. With this limitation, the proposed formula is successfully applied also to
mixtures at higher than normal values of initial pressure (up to 10 atm) and temperature (up to 400 K).
䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen–methane blends; Laminar burning velocity; Le Chatelier’s Rule

1. Introduction
Hydrogen–methane blends are receiving attention as alterna-
tive fuels for power generation applications for two main rea-
sons. The first reason is related to the opportunity of adding
hydrogen to methane in order to improve performance, to ex-
tend operability ranges and to reduce pollutant emissions of
lean combustion in both stationary [1–5] and mobile [6–9] sys-
tems. The second reason is due to concerns about global warm-
ing and the prospect of using hydrogen in both, fuel cells and
combustion devices [10–13]. However, stringent problems of
safety and storage strongly complicate the use of pure hydro-
gen. To bypass these difficulties, substitution of hydrogen with
methane or other hydrocarbons has been proposed as an interim
solution towards a fully developed hydrogen economy [14].
The effective and safe use of hydrogen–methane mixtures
requires that the physiochemical properties of such hybrid fuels
have to be determined. In particular, knowledge about laminar
∗ Corresponding author. Tel.: +39 81 7682947; fax: +39 81 7622915.
E-mail address: dibenede@irc.na.cnr.it (A.Di. Benedetto).
hybrid flames has to be acquired, not only for laminar propa-
gation itself, but also for the understanding of turbulent flames.
In most practical applications as well as in explosions, turbu-
lent premixed flames are involved that may be considered as
a set of stretched laminar-like flamelets whose characteristics
are the fundamental input parameters for modeling turbulent
combustion [15–17].
The laminar burning velocity of hydrogen–methane/air
premixed flames has been experimentally measured at dif-
ferent values of equivalence ratio and fuel composition
[14,18–25].
In 1959 Scholte and Vaags [18] carried out the first mea-
surements by means of the tube burner method. Together with
the more recent work by Liu et al. [22], this is the most ex-
tensive experimental study since it investigates a wide range
of equivalence ratios at hybrid fuel compositions varying from
pure methane to pure hydrogen. All the other experimental
papers may be classified into two categories. The first deals
with the study of the effect of hydrogen addition to methane
[20,21,23–25] and the second with the effect of substitution of
hydrogen by methane [14,19].

0360-3199/$ - see front matter 䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.05.016
638 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646
Nomenclature
A normalized stream tube cross-sectional area in
Eq. (1)
CA air mole fraction in the unburned mixture in
Eqs. (10) and (11)
CF methane mole fraction in the unburned mixture
in Eqs. (10) and (11)
CS hydrogen mole fraction in the unburned mix-
ture in Eqs. (10) and (11)
ki pre-exponential factor in Arrhenius kinetics of
the elementary step i in Eq. (3)
M total mass flow rate in Eq. (1)
NTP normal temperature and pressure
R2 regression factor
RH relative amount of hydrogen addition to
methane defined according to Eq. (11)
SF i sensitivity factor of methane mole fraction to
the elementary reaction step i defined accord-
ing to Eq. (3)
Sl laminar burning velocity, cm/s
Sl_CH4 laminar burning velocity of pure methane in
Eqs. (2) and (14), cm/s
Sl_CHEMKIN laminar burning velocity calculated by means
of CHEMKIN simulations, cm/s
According to these results when hydrogen is added to
methane, a linear increase of the laminar burning velocity
occurs with increasing the hydrogen mole fraction in the fuel
(XH2 ) up to values equal to about 0.7. Furthermore, the en-
hancement is slight, especially at lower equivalence ratios. On
the contrary, at high hydrogen molar contents (XH2 > 0.85),
methane addition has a strong inhibiting effect on hydrogen
reactivity. On increasing the methane content, a linear decrease
takes place that becomes steeper at rich conditions.
The experimental results obtained by Sierens and Rosseel
[8] on an internal combustion engine using lean blends of
natural gas and hydrogen, are consistent with the effects of
the addition of hydrogen and methane on the hybrid mixtures
laminar burning velocity. In particular, they have shown that
there is a very limited improvement in the engine efficiency
and emissions for hydrogen molar contents in the fuel up to
20%. On the other hand, high efficiency and low emissions
without abnormal combustion (backfire and knock) have been
found starting from hydrogen substitutions by natural gas equal
to 20% (mol).
On the computational side, simulations of the premixed hy-
brid flames have been performed extensively [14,23–31]. Most
of these computations were carried out with the CHEMKIN
[32] or the COSILAB [33] laminar premixed flame codes in
which detailed kinetic schemes were implemented [34,35].
These efforts are aimed at reproducing experimental results
and to gain insight. There is an agreement that chemical effects
dependent on H radicals play a role in both, the promoting effect
Sl_H2 laminar burning velocity of pure hydrogen in
Eqs. (2) and (14), cm/s
Sl_LC laminar burning velocity evaluated according
to the Le Chatelier’s Rule-like formula (14),
cm/s
Sl_linear laminar burning velocity evaluated according to
the linear combination of Eq. (2), cm/s
XH2 hydrogen mole fraction in the hybrid fuel in
Eqs. (2) and (14)
xCH4 methane mole fraction in the reactive mixture
in Eq. (3)
Greek symbols
 ratio between the maximum value of the H rad-
ical mole fraction in the reaction zone and the
corresponding value for pure methane/air flame
 fuel equivalence ratio
F effective methane equivalence ratio defined ac-
cording to Eq. (10)
u unburned mixture density in Eq. (1)
 laminar burning velocity normalized by the cor-
responding value for pure methane/air flame
of hydrogen addition on methane combustion [24,26,27,29,30]
and the inhibiting effect of methane on hydrogen [28].
All the cited works deal with the simulations of laminar
flames on the methane rich side [23–27,29–31] or on the hy-
drogen rich side [14,28], without identifying a global behavior.
In particular, no theoretical studies of the laminar burning ve-
locity at intermediate hydrogen molar content in the blend have
been performed to clarify how the transition between the two
extreme behaviors takes place.
Up to now, correlations for evaluating the laminar burning
velocity of hydrogen–methane/air mixtures as a function of
equivalence ratio and fuel composition have been proposed by
Yu et al. [21] and El-Sherif [30] only for the low hydrogen
content side.
It is not yet established how to calculate the laminar burning
velocity at intermediate and high hydrogen contents. Indeed,
the behavior of the hybrid mixtures laminar burning velocity is
not easy, and raises the question whether the laminar burning
velocity may be obtained from the values of the individual
constituents at the same conditions by varying the hydrogen
content in the blend.
The objectives of the present theoretical work are,
therefore, (i) to calculate the laminar burning velocity of
hydrogen–methane/air flames over a wide range of unburned
mixture compositions; (ii) to clarify the effects of radicals
interactions on the observed trends; (iii) to obtain a correla-
tion for the laminar burning velocity at different values of
equivalence ratio and hydrogen content in the fuel.
 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646
2. Model description and validation
The calculation of the laminar burning velocities of
hydrogen–methane/air mixtures was carried out by means of
simulations of the one-dimensional, planar, adiabatic, steady,
unstretched, laminar flame propagation. The Sandia PREMIX
module [32] of the CHEMKIN package was used by imple-
menting the detailed reaction scheme GRI-Mech version 3.0
[34].
The code that adopts a hybrid time-integration/Newton-
iteration technique to solve the steady-state mass, species,
and energy conservation equations, was set up to simulate a
freely propagating flame with mixture-averaged formulas for
evaluating the transport properties.
Initial and boundary conditions were assigned to define the
problem environment.
The initial flow rate of the unburned mixture was chosen
equal to 0.04 g/cm2 s, according to the measurement of stoi-
chiometric methane/air flame speed by Egolfopoulos et al. [36].
To start the iteration the temperature profile estimation obtained
by Van Maaren et al. [37] for a stoichiometric methane/air flame
was adopted, as suggested by Uykur et al. [31]. The temper-
ature profile resulting from the first simulation step was used
for the next step.
At the inlet boundary temperature (300 K), pressure (1 atm)
and composition of the unburned mixture were assigned.
At the exit boundary it was specified that all gradients
vanish.
As shown by Smooke et al. [38], for freely propagating
flames the total mass flow rate (M) is an eigenvalue solution
of the physical problem that has to be determined. Therefore,
an additional constrain is required that was assigned by fixing
the location of the flame, and in particular, the point at which
the flame temperature reaches 400 K. The distance of the point
was calculated from the initial temperature profile estimation
of the code. This choice assures that, for all the investigated
flames, the species and temperature gradients nearly vanish at
the inlet. Indeed, if this condition is not met some heat is lost
through the inlet boundary, thus decreasing the total mass flow
rate [39].
The laminar burning velocity (Sl ) was obtained from the
continuity equation (1):
M = u Sl A,
where u is the unburned mixture density and A is the cross-
sectional area of the stream tube encompassing the flame nor-
malized by the burner area. A was assumed to be constant along
the spatial coordinate and equal to unity.
In the computations the windward differencing on both
convective and diffusion terms was used. The gradient and
curvature values were fixed equal to 0.2. The total length of
the calculation domain, starting 2 cm upstream of the reac-
tion zone, was chosen equal to 12 cm. Further increases in
mesh resolution and domain-size resulted in less than 1 cm/s
difference in the calculated flame speeds.
Ren et al. [23,24] implemented the GRI-Mech in the
PREMIX code and validated this kinetic mechanism for
639
hydrogen–methane blends by comparing the computed values
of the laminar burning velocity with experiments at low values
of equivalence ratio (0.63  0.73) and of hydrogen mole
fractions in the fuel (0 XH2 0.08).
In the present work further validation of the reaction mecha-
nism was attempted for stoichiometric and rich conditions and
at higher hydrogen contents in the hybrid mixtures.
Only stretch-free data obtained at NTP conditions were
used [14,21,25]. The experiments by Law and Kwon [14]
were conducted at equivalence ratio values equal to 0.6, 1 and
1.67 and at high values of hydrogen molar content in the fuel
(0.85 XH2 1). The measurements by Yu et al. [21] were ob-
tained at equivalence ratios and hydrogen mole fractions in the
fuel varying in the ranges 0.51 1.37 and 0 XH2 0.7,
respectively. The recent experiments by Halter et al. [25] were
carried out at equivalence ratios ranging from 0.7 to 1.2 and
hydrogen mole fractions up to 0.2.
Law and Kwon [14] and Halter et al. [25] used the flow
configuration of the outwardly propagating spherical flame.
Yu et al. [21] adopted a symmetrical, adiabatic counterflow
twin-flame arrangement. For this type of flow configuration,
Vagelopoulos et al. [40] have shown that if the nozzle sepa-
ration distance is too short, the laminar burning velocity can
be overestimated. Indeed, as reported by Halter et al. [25] the
comparison between their results and the ones by Yu et al. [21]
confirms this trend. However, in the literature the data by Yu
et al. [21] are the only stretch-free results covering the range
0.20 < XH2 0.7.
Fig. 1 shows the experimental versus the calculated laminar
burning velocities. A good agreement is found except at high
hydrogen contents. This is probably related to the used kinetic
scheme. The maximum error is reached for the stoichiometric
pure hydrogen flame and it is about 15%. However, we do think
that this error is not able to significantly affect all the results
and conclusions of the paper.
350
Law & Kwon [14]
300 Yu et al. [21]
Halter et al. [25]
(1) 250
Model results
200
150
100
50
0
0 50 100 150 200 250 300
Experimental results
Fig. 1. Model versus experimental results of the laminar burning velocity of
hydrogen–methane/air mixtures (cm/s), at NTP conditions.
640 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646

Sl linear interpolation tions. This implies the presence of strong non-linear effects in
80 chemical kinetics that emphasize the weight of the more slowly
I regime II regime III regime
reacting methane in the composite fuel combustion.
60 φ =0.6 From Fig. 2, at all the equivalence ratios, it is possible to
Sl (cm /s)

identify three regimes in the hybrid flame propagation depend-

40 ing on the hydrogen mole fraction in the fuel.
At low hydrogen contents (0 < XH2 < 0.5), a regime of
20 methane-dominated combustion takes place being character-
ized by a linear and slight increase of the methane laminar
300 burning velocity on adding hydrogen.
At high hydrogen contents (0.9 < XH2 < 1), a regime of
φ =1
methane-inhibited hydrogen combustion occurs corresponding
Sl (cm /s)

200 to a linear and sharp decrease of the hydrogen laminar burning

velocity on increasing the methane presence in the fuel.
The two linear trends found in both these regimes have been
100 widely recognized in the literature.
At intermediate hydrogen mole fractions (0.5 XH2 0.9),
a transition regime is found.
400
In order to get insight into the role of radicals interactions in
φ =1.5 the observed behaviors, a sensitivity analysis was performed. In
300
particular, the methane mole fraction sensitivity factors, defined
Sl (cm /s)

according to
200
ki jxCH4
SF i = , (3)
100 xCH4 jki
were calculated, thus evaluating the major steps affecting the
0
0.0 0.2 0.4 0.6 0.8 1.0 combustion of the blends.
XH
2
The factors lower than −2 and higher than 2 are plotted in
Fig. 3 by varying the hydrogen content at the three equivalence
Fig. 2. Laminar burning velocity of hydrogen–methane/air mixtures as func- ratios of Fig. 2.
tion of the hydrogen content at three values of the equivalence ratio, at NTP It results that the following elementary reaction steps con-
conditions. tribute to the kinetic control of the hybrid mixture combustion:

H + O2 + H2 O ⇔ HO2 + H2 O, (4)
3. Results and discussion
H + O2 ⇔ O + OH, (5)
3.1. Laminar burning velocity calculations and sensitivity
analysis OH + CO ⇔ H + CO2 , (6)

OH + CH4 ⇔ CH3 + H2 O, (7)

The laminar burning velocities of hydrogen–methane/air
mixtures at 300 K and 1 atm were calculated by varying the
equivalence ratio from lean to rich conditions and the fuel
composition from pure methane to pure hydrogen.
In Fig. 2 the computed values (Sl ) are plotted versus the
hydrogen mole fraction in the fuel (XH2 ), at three values of
equivalence ratio ( = 0.6; 1; 1.5). In the same plot the linear
combination of the laminar burning velocity of the pure fuels
is also shown, calculated as follows:
Sl_linear (, XH2 ) = Sl_H2 () · XH2
+ Sl_CH4 () · (1 − XH2 ),
where Sl_H2 and Sl_CH4 are the laminar burning velocity of
hydrogen and methane evaluated at the same equivalence ratio
of the hybrid fuel ().
It appears that the computed values of the mixture laminar
burning velocity are always well below those obtained by aver-
aging the flame speeds of the constituent gases in molar propor-
H + CH4 ⇔ CH3 + H2 , (8)
H + CH3 + (M) ⇔ CH4 + (M). (9)
However, the above listed steps are not simultaneously in-
volved by varying the equivalence ratio. At lean conditions re-
action (8) does not play any role as well as steps (4) and (6)
for stoichiometric mixtures. Moreover, at rich conditions only
steps (5), (8) and (9) hold.
In the first regime (0 < XH2 < 0.5), independently from
(2) stoichiometry, the methane conversion is dominated by step
(5) whose relevance in hydrocarbons combustion is well
documented in the literature [24,26,27,30,41,42]. For lean
methane/air flames with small hydrogen addition, Ren et al.
[24] have found that methane is mainly consumed via reaction
(7) that requires hydroxyl radicals OH, thus explaining the
high sensitivity of the burning rate to step (5). Accordingly,
in a recent work Dagaut and Nicolle [42] have shown that for
 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646 641

H+CH3+(M)=CH4+(M) φ=0.6

xH =0.95
H+CH4 =CH3+H2 2
xH = 0.9
2
xH = 0.85
2
OH+CH4 = CH3+H2O xH = 0.7
2
xH = 0.5
2
xH = 0.3
2
OH+CO =H+CO2 xH = 0
2

H+O2 =O+OH

H+O2+H2O=HO2+H2O

-10 -8 -6 -4 -2 0 2 4 6

φ=1
H+CH3+(M)=CH4+(M)

H+CH4=CH3+H2 xH =0.95
2
xH = 0.9
2
xH = 0.85
2
OH+CH4 =CH3+H2O xH = 0.7
2
xH = 0.5
2
xH = 0.3
2
OH+CO=H+CO2 xH = 0
2

H+O2 = O+OH

H+O2+H2O= HO2+H2O

-10 -8 -6 -4 -2 0 2 4 6

H+CH3+(M)=CH4+(M) φ=1.5

H+CH4 = CH3+H2

xH =0.95
2
OH+CH4 = CH3+H2O xH = 0.9
2
xH = 0.85
2
xH = 0.7
OH+CO=H+CO2 2
xH = 0.5
2
xH = 0.3
2
H+O2 = O+OH xH = 0
2

H+O2+H2O= HO2+H2O

-10 -8 -6 -4 -2 0 2 4 6

Fig. 3. Sensitivity factors of the methane molar fraction as function of the hydrogen content at three values of the equivalence ratio, at NTP conditions.

lean hydrogen-enriched natural gas blends, the methane com-
bustion mostly proceeds through reactions with OH radicals.
Moreover, they have found that the main agent of methane
oxidation is reaction (7) and their sensitivity analysis also
confirms the importance of step (5) among those forming
OH radicals.
In the second regime (0.5 XH2 0.9), the sensitivity factors
of step (5) decrease and assume values comparable or lesser
than those corresponding to the other steps. More precisely, at
all the equivalence ratios, starting from hydrogen mole fraction
values equal to 0.7–0.85, step (5) does not play anymore the
main role in controlling the methane combustion.
642 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646

12 accelerates the overall rate of combustion by increasing the

φ=0.6
H radicals concentration and, then, the net amount of chain
10 branching from this step. However, the increase of the laminar
σ
burning velocity is still slight, the H radicals pool being not
8 αH
sufficiently increased.
σ or α H

6 A significant enhancement of the laminar burning velocity

coupled to that of the H radicals concentration occurs only start-
4 ing from hydrogen mole fraction values higher than about 0.5
and, then, starting from the second regime when the sensitivity
2 factors of step (5) decrease. Consequently, it comes down that
8 only at these values of fuel compositions the methane request
of H radicals can be compensated by the hydrogen presence in
φ=1.0 the blend.
6 From Fig. 4 it turns out that, whatever the hydrogen con-
tent in the mixture, the increase of the laminar burning velocity
σ or α H

4 compared to methane flames is equal to that of the H radicals

concentration only at stoichiometric conditions. On the con-
trary, it is lower for non-stoichiometric mixtures with hydrogen
2 mole fraction values higher than 0.5.
This can be explained by the fact that H radicals also partic-
ipate in the termination reactions (4) and (9) that compete for
80
H atoms with the chain branching reaction (5) at lean and rich
φ =1.5 conditions, respectively. The sensitivity factors of both these
steps are positive, as reported in Fig. 3, since they obstruct the
60
methane conversion through subtraction of H atoms.
σ or α H

Fig. 3 shows that at stoichiometric conditions step (4) is

40
20
0.0 0.2 0.4 0.6 0.8 1.0
XH
2
Fig. 4. Normalized laminar burning velocity () and maximum H concentra-
tion in the reaction zone (H ) as function of the hydrogen content at three
values of the equivalence ratio, at NTP conditions.
In the third regime (0.9 < XH2 < 1), step (7) kinetically dom-
inates the lean combustion, while step (8) controls both the
stoichiometric and rich flames.
Fig. 4 shows the laminar burning velocity () and the maxi-
mum value of the H radicals mole fraction in the reaction zone
(H ), both normalized by means of the corresponding values
for pure methane flames, as function of the hydrogen content
at different equivalence ratios.
It appears that the burning velocity of the blends and the H
radicals concentration are strictly related,  following the H
trend.
In particular, up to hydrogen mole fractions equal to 0.5 and,
then, in the first regime  is very close to H at all the equiva-
lence ratios, meaning that both the laminar burning velocity and
the maximum H atoms concentration with respect to the case
of pure methane flames increase almost by the same factors.
Since step (5) controls the methane conversion in this
regime, it can be deduced that the hydrogen addition to methane
not involved, while step (9) plays a little role only for low
hydrogen contents. This suggests that, with respect to lean and
rich flames, at stoichiometric conditions H atoms are much
more inclined to consume methane rather than to be involved in
the reactions (4) and (9) which decrease the global reactivity. It
is saying that for a lean hydrogen–natural gas blend Dagaut and
Nicolle [42] have also evidenced the relevant effect of reaction
(4) on slowing down the methane oxidation.
In Fig. 4 it appears that the differences between  and H are
higher at rich rather than at lean conditions. Fig. 4 also shows
that, for the same fuel composition, the H radicals concentration
is greater in the rich flames rather than in the lean flames. Then,
a larger fraction of H atoms can be lost by the reaction with CH3
radicals (9) at rich conditions compared to that participating in
the reaction (4) at lean conditions.
From Fig. 4 it results that in the third regime, starting from
pure hydrogen and increasing the amount of methane added in
the fuel, a sharp decrease of both  and H takes place at all
the equivalence ratios.
In the literature it is well known that the high burning velocity
of hydrogen/air premixed flames are due to the occurrence of
fast exothermic reactions in the low temperature flame regions
that require H atoms furnished by diffusion from the flame front
according to the propagation mechanism of such flames [28,43].
In contrast, methane/air premixed flames propagate thanks to
the thermal energy transported by conduction from the high to
the low temperature regions, hence having much lower flame
speeds [43].
In the third regime, hydrogen substitution by methane leads
to the removal of H radicals and, then, to the inhibition of the
hydrogen combustion.
 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646
Table 1
Normalized slopes of the linear trends of the laminar burning velocity on
increasing the hydrogen mole fraction in the fuel at the methane rich side
and on decreasing the hydrogen mole fraction at the hydrogen rich side
 Slope of  at the Slope of  at the
methane rich side hydrogen rich side
0.6 0.87 −17.6
1 1.05 −21.3
1.5 2.14 −129.3
The consumption of H radicals due to methane addition to
hydrogen takes place by means of steps (8) and (9). The former
involves the direct reaction of H atoms with methane to give
CH3 radicals. In step (9) H atoms react with CH3 radicals
produced by the kinetically controlling reactions that are steps
(7) and (8) at lean and rich conditions, respectively, and both
for stoichiometric flames.
For the three explored equivalence ratios, the slopes of the
linear trends of  are reported in Table 1 on increasing the
hydrogen mole fraction in the fuel at the methane rich side
(positive values) and on decreasing the hydrogen mole fraction
at the hydrogen rich side (negative values).
In qualitative agreement with the literature results, it appears
that the addition of hydrogen to methane has a weaker pro-
moting effect with lean mixtures, while the inhibiting effect of
methane on hydrogen is stronger at rich conditions.
These trends are related to the observed strong dependence
of the laminar burning velocity of the blend on H radicals.
They can be explained by considering that, whether increas-
ing or decreasing the hydrogen mole fraction in the fuel starting
from a fixed composition, the corresponding variations of the H
radicals concentration are higher on increasing the equivalence
ratio.
Furthermore, the significant relevance of step (4) on the over-
all reaction of lean mixtures with low hydrogen contents, evi-
denced in Fig. 3, also contributes to the less efficient increase of
the laminar burning velocity with hydrogen addition observed
on decreasing the equivalence ratio.
On the other side, at high hydrogen contents the greater sen-
sitivity of the methane conversion at rich conditions to steps
(8) and (9) compared to that of lean and stoichiometric flames
to steps (7) and (8) (see Fig. 3) enhances the inhibition of the
blend combustion by hydrogen substitution with methane on
increasing the equivalence ratio.
More precisely, in this fuel composition range the lower
presence of oxygen in the rich flames compared to lean and
stoichiometric conditions allows the formed CH3 radicals ac-
celerating the termination step (9) with respect to the oxidation
reactions. This determines the subsequently more significant
decrease of the burning velocity of rich mixtures.
3.2. Correlation of the laminar burning velocity
A correlation for evaluating the laminar burning velocity
of hydrogen–methane/air mixtures at NTP conditions as a
function of equivalence ratio and fuel composition has been
643
proposed by Yu et al. [21] for hydrogen mole fraction in the
fuel up to 0.7. The authors have been able to linearly corre-
late the laminar burning velocity of the hybrid flames with
the burning velocity without hydrogen addition and a single
parameter indicating the extent of the hydrogen content. More
precisely, hydrogen has been considered to be present only in
stoichiometrically small quantities, its combustion requiring
four times less oxygen than methane. Consequently, they have
assumed that there is enough air to facilitate a complete oxi-
dation of hydrogen, while the remaining air is used to oxidize
methane. An effective methane/air equivalence ratio, F , has
been therefore defined as follows:
CF /[CA − CH /(CH /CA )st ]
F = , (10)
(CF /CA )st
while the relative amount of hydrogen addition, RH , has been
expressed according to
CH + CH /(CH /CA )st
RH = , (11)
CF + [CA − CH /(CH /CA )st ]
where CA , CF and CH are the initial mole fractions of the
air, methane and hydrogen, respectively (the subscript ‘st’ de-
notes the stoichiometric conditions). In the explored ranges of
F (0.51.1.37) and RH (0.0.5), the laminar burning velocity
(Sl ) has been then correlated by the following equation:
Sl (F , RH ) = Sl (F , 0) + 0.8RH (m/s). (12)
More recently, El-Sherif [29] has numerically reproduced the
experimental results by Yu et al. [21] at F ranging from 0.62
to 1.2 and RH varying up to 0.4. In this parameters range he
has proposed the following correlation:
Sl (F , RH ) = 0.38−0.35
F exp[−5.5(F − 1.1)2 ]
+ 0.84RH (m/s), (13)
with F and RH defined according to (10) and (11), respec-
tively. Eq. (13) is similar to Eq. (12), but it presents the explicit
dependence of the laminar burning velocity without hydrogen
on the fuel/air equivalence ratio (F ).
Eqs. (12) and (13) are able to take into account the linear
trend of the laminar burning velocity with hydrogen addition
on the methane rich side. Due to the expressions of the param-
eters F and RH defining the composition of the hybrid fuel/air
mixtures, these equations are intrinsically valid only for low
hydrogen contents.
In order to obtain a correlation of the laminar burning ve-
locity of hydrogen–methane/air mixtures valid also at interme-
diate and high hydrogen contents and at different values of
equivalence ratio, we tested the feasibility of a Le Chatelier’s
Rule-like formula expressed according to
Sl_LC (, XH2 )
1
= . (14)
XH2 /Sl_H2 () + (1 − XH2 )/Sl_CH4 ()
In Figs. 5 and 6 the laminar burning velocity as calculated by
means of Eq. (14). (Sl_LC ) is plotted versus the value obtained
644 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646

300 300
φ≤1 Simulations
250 Le Chatelier's Rule
250 xH = 0.95
2
Sl_LC (cm/s)

200
200
150

Sl (m / s)
x = 0.85
H2

100 150
P = 1 atm
P = 5 atm xH = 0.7
50 100 2
P = 10 atm
300
φ >1 50 xH = 0.5
2
250
xH = 0.1
2
200
Sl_LC (cm/s)

0.5 1.0 1.5 2.0 2.5 3.0

150 φ

100 Fig. 7. Computed and correlated values of the laminar burning velocity as
function of the equivalence ratio at different values of the hydrogen content,
50 at NTP conditions.

0
50 100 150 200 250 300
Sl_CHEMKIN (cm /s)
at all the pressure and temperature values investigated the re-
gression factors, R 2 , are equal to 0.995 at  1 and to 0.83
Fig. 5. Laminar burning velocity calculated with Eq. (14) versus computed at  > 1. As a consequence, at lean and stoichiometric con-
values at P = 1, 5 and 10 atm and at T = 300 K. ditions, the agreement is quite good, whatever the hydrogen
content. On the contrary, with rich mixtures, more significant
differences between the simulations results and the values
300 predicted by Eq. (14) can be observed.
φ ≤1 Fig. 7 shows the laminar burning velocity at different values
250
of hydrogen content in the fuel (XH2 = 0.1; 0.5; 0.7; 0.85 and
0.95) versus the equivalence ratio, as obtained by means of the
Sl_LC (cm/s)

200
CHEMKIN computations and of Eq. (14) at P = 1 atm and
150 T = 300 K. It appears that at lean and stoichiometric conditions
100
a good prediction is obtained. This applies also to the rich
T=300 K mixtures with low hydrogen contents (XH2 < 0.7).
50 T=350 K The obtained results are consistent with the findings on the
T =400 K
flammability limits of hydrogen/methane mixtures by Wierzba
300
and coworkers [44–46]. These authors have experimentally
φ >1 evaluated the lean [44] and rich [45,46] limits in air for upward
250
vertical flame propagation at atmospheric pressure. They have
Sl_LC (cm/s)

200
investigated the entire composition range of the hybrid fuel by
150 comparing the measured values with those calculated accord-
ing to the Le Chatelier’s Rule. Interestingly, they have observed
100 that the Le Chatelier’s Rule well reproduces the lower flamma-
bility limits, while the rich limits can be accurately predicted up
50
to a hydrogen percentage in the fuel equal to about 70% molar.
We do think that differently from the linear formula (2),
50 100 150 200 250 300
the Le Chatelier’s Rule-like formula (14) is able to take into
Sl_CHEMKIN (cm /s) account the kinetic interaction between radicals. However, at
rich conditions when dealing with high hydrogen (and then H
Fig. 6. Laminar burning velocity calculated with Eq. (14) versus computed radicals) contents the interaction is too strong to be reproduced
values at P = 1 atm and at T = 300, 350 and 400 K.
by Eq. (14) and a more sophisticated formula is required.

by means of simulations (Sl_CHEMKIN ) for lean and stoi- 4. Conclusions

chiometric conditions ( 1) and for rich conditions ( 1)
at different values of inlet pressure (1, 5 and 10 atm) and The laminar burning velocities of methane–hydrogen/air pre-
temperature (300, 350 and 400 K), respectively. It results that mixed flames were calculated by means of the CHEMKIN
 V. Di Sarli, A.Di. Benedetto / International Journal of Hydrogen Energy 32 (2007) 637 – 646
PREMIX code implementing the GRI-Mech detailed reaction
mechanism. A wide range of blends compositions was explored
at 300 K and 1 atm.
It is found that the values of the laminar burning velocity
are always smaller than the ones obtained by averaging the
corresponding values of the pure fuels in molar proportions.
Moreover, three regimes are identified in the hybrid flame
propagation depending on the hydrogen mole fraction in the
fuel: (1) methane-dominated combustion (0 < XH2 < 0.5); (2)
transition (0.5XH2 0.9); and (3) methane-inhibited hydro-
gen combustion (0.9 < XH2 < 1).
In both regimes (1) and (3) the laminar burning velocity
increases linearly with increasing the hydrogen molar content
of the blend.
In regime (1), the enhancement of the methane laminar burn-
ing velocity by hydrogen addition is slight, especially with lean
mixtures. In regime (3) methane substitution to hydrogen has
a significant decreasing effect on flame speed. This becomes
stronger at rich conditions.
All these findings are ascribed to the amount of H radicals and
their fate through the chain branching and termination reaction
steps.
A Le Chatelier’s Rule-like formula was used to correlate the
calculated values of the mixtures laminar burning velocity. A
good prediction is obtained in all the regimes at lean and stoi-
chiometric conditions and in the first regime for rich mixtures.
This agreement is also found for the computational results of
mixtures at higher than normal values of initial pressure (up to
10 atm) and temperature (up to 400 K).
In the validity ranges, the proposed correlation is of practical
importance as it can be used in turbulent modelling.
Acknowledgments
The authors thank Prof. Gennaro Russo for useful scientific
discussions.
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