Fuel 86 (2007) 585–596

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Burning velocity of methane/diluent mixture with reformer gas addition

Panfeng Han 1, M. David Checkel, Brian A. Fleck, Natalie L. Nowicki *

Department of Mechanical Engineering, University of Alberta, Edmonton, Canada T6G 2G8

Received 24 January 2006; received in revised form 28 July 2006; accepted 2 August 2006
Available online 12 September 2006

Abstract

The motivation of this study is to explore the feasibility of extending the EGR (exhaust gas recirculation) diluent tolerance for meth-
ane/air mixtures with reformer gas (CO and H2). A preheated cylindrical combustion chamber was used to measure the laminar burning
velocity of methane/air mixture with variations of EGR diluent, reformer gas, temperature and pressure. The experiments were carried
out at the range of initial temperature from 298 K to 498 K and initial pressure from 1 atm to 5 atm. The maximum EGR fraction is 40%.
Reformer gas was introduced to raise the burning velocity of methane/EGR mixture to the undiluted level. Results indicate that the
reformer gas has potential to improve the burning velocity while reducing the nitric oxide emission.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Exhaust-gas-recirculation; Reformer-gas; NOx

1. Introduction Unfortunately, EGR slows down the burning velocity.

The automotive industry faces steady pressure from the
public and government to reduce vehicle emissions because
vehicles are a significant source of urban pollution. Oxides
of nitrogen (NOx) produced by vehicles accounted for 49%
of US national NOx emission in 2002 [1] EGR (exhaust gas
recirculation) has been developed to effectively reduce the
NOx emission by lowering the combustion temperature
[2–4] and diluting the oxygen concentration in intake mix-
tures [3]. It has been found that 10–25% EGR is able to
substantially decrease NOx concentrations [4]. Sasaki
et al. [5] investigated the effects of EGR on a direct injec-
tion gasoline engine and found that a large volume EGR
(about 30%) reduced NOx to an extremely low level of 1/
20 of the base value under stable ignition. EGR also
reduces the heat transfer rate from the cylinder contents
to the surrounding surface and lowers specific fuel con-
sumption [4].
*
Corresponding author.
E-mail address: nnowicki@ualberta.ca (N.L. Nowicki).
1
Currently at Cummins Corporation Beijing Branch, Suite 908 World
China Tower 1, No.1, Jian Guomen Wai Dajie, Beijing, China.
Lower burning velocity works against ideal combustion
stability and leads to increased heat loss, lower combustion
efficiency and misfire. These problems decrease the maxi-
mum power of the engine [3,6] and the indicated work pro-
duced from a given mass of air/fuel mixture [7]. Selim [8]
found that the thermal efficiency and rate of pressure rise
declined with over 5% EGR in a dual fuel engine. Increas-
ing EGR also has been shown to reduce fuel economy and
hydrocarbon emission due to occurrence of misfire [5].
These combustion problems restrict the tolerance of EGR
and the potential benefits of a high volume of EGR. To
overcome these problems, hydrogen is considered as an
ideal fuel to raise the burning velocity and extend the
EGR tolerance. For example, in a natural gas engine,
20% additional hydrogen broadened the EGR tolerance
from 8% to 25% while retaining the stable combustion
and low emissions [9]. Swain et al. [10] indicated that a mix-
ture of 20% hydrogen and 80% methane reduced problems
with flame initiation and propagation. In addition, even a
small amount of hydrogen significantly decreases hydro-
carbon emission and cycle-by-cycle variability [11].
The demands of production, distribution and storage
of hydrogen on a vehicle are challenging in spite of

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.08.011
586 P. Han et al. / Fuel 86 (2007) 585–596
hydrogen’s advantages. Therefore, on-board fuel reform-
ing that converts hydrocarbon fuel to reformer gas, such
as hydrogen and carbon monoxide, has been developed
to meet the demands. Tully and Heywood found that refor-
mer gas raised the peak net indicated fuel conversion effi-
ciency 12% while cutting NOx emissions 94% at the peak
efficiency point compared to data obtained from a gasoline
engine operating stoichiometrically [12]. In summary, the
reformer gas is able to potentially broaden the tolerance
of EGR and maintain combustion stability.
The laminar burning velocity is a fundamental parameter
required to understand the combustion process and flame
propagation. It is also a necessary input to model turbulent
combustion and pollutant formation. Precise values of lam-
inar burning velocities are useful for practical applications
on internal combustion engines, which operate at pressures
varying from 5 atm to 60 atm and unburnt gas temperature
ranging from 500 K to 1100 K [13]. In other studies, the
burning velocities and flammability limits of n-butane and
iso-butane with reformer gas addition were analyzed at
room temperature [14]. In addition, the effects of reformer
gas on engine performance and characteristics at near dilu-
ent limit and lean mixture were also investigated [12,15].
However, all of these studies were focused on gasoline or
partial oxidation reaction, and data for burning velocities
of methane/EGR/reformer gas mixtures is scarce, especially
at elevated temperature and pressure to simulate real engine
operation. The burning velocity at elevated temperature
and pressure is more useful in understanding the effects of
diluents and reformer gas. Furthermore, an interesting
question remains whether the methane/EGR/reformer gas
mixture loses the potential of low NO emission while main-
taining the undiluted burning velocity.
Methane, a major component of natural gas, was used in
this study for experimental practicality and potential appli-
cation in natural gas engines. The high octane rating, low
level of non-hydrocarbon impurities and low carbon/
hydrogen ratio of methane provide the natural gas engine
fundamental emission advantages [8]. However, the natural
gas engine has undesirably high NO emissions [9] despite
thorough development [16,17]. Thus, EGR is essential for
a methane-fueled engine. Unfortunately, compared with
gasoline and methanol-fueled engines, the methane-fueled
engine’s EGR tolerance is the poorest [7]. Specifically, a nat-
ural gas engine running at IMEP of 2 atm and 2000 rpm has
a maximum EGR tolerance of 8% [9]. Therefore, reformer
gas is necessary to broaden the methane-fueled engine’s
EGR tolerance and improve its combustion stability.
This study focuses on the stoichiometric mixtures used
with 3-way catalyst systems, though engines operating with
lean mixture have greater efficiency [12], lower flame tem-
perature and reduced NOx emission. Their lower flame
temperature leads to low chemical heat release rates and
thus the loss of maximum power. Stoichiometric mixtures
are comparatively worse than lean mixtures in NOx emis-
sions, but 3-way catalytic converters require the exhaust
gas of stoichiometric combustion for the best effectiveness
and efficiency. Overall, when considering both NOx emis-
sion and torque output, stoichiometric mixtures with
EGR produced nearly 30% more torque than lean-burn
mixtures and low NOx emission (<10 ppm) in a hydro-
gen-fueled engine [18]. It is for this reason that stoichiom-
etric mixtures were used in the present work.
Houseman and Cerini studied the possibility of onboard
steam reforming of gasoline or methanol to generate
hydrogen for automobiles and demonstrated that it is tech-
nically feasible [19]. A catalyst, such as Ni-YSZ, is strongly
recommended to reduce the reaction temperature of meth-
ane steam reforming [20,21]. Chen et al. produced a large
volume of hydrogen at a relatively low temperature by
using an improved novel membrane reformer to stimulate
the steam reforming of methane [22]. The review by Jamal
and Wyszynski [23] found that steam reforming generated
the maximum quantity of hydrogen compared to other
methods of hydrogen production, and did not involve
nitrogen. Despite using an exothermic reaction, another
method of hydrogen production, partial oxidation, pro-
duced less hydrogen than steam reforming. In particular,
partial oxidation of gasoline yields one quarter hydrogen,
one quarter carbon monoxide, and one half nitrogen
[12,15]. Additional CO was found to be slightly effective
in improving combustion efficiency, emissions and stability
[12]. Steam reforming has relatively low costs, compara-
tively high efficiency, and it is able to ideally produce the
maximum amount of hydrogen, 75% [24]. Thus, steam
reforming’s hydrogen-rich products were used for these
experiments. The reformer gas was simulated by a mixture
of H2 and CO with volumetric ratio of 3:1, which corre-
sponded to the ideal products of steam reforming of meth-
ane as shown in
CH4 + H2 O = CO + 3H2 ð1Þ
2. Experimental apparatus and method
2.1. Combustion chamber
A combustion chamber designed by Checkel et al. [25]
employing a preheated high-pressure cylinder with central
spark ignition was used. The chamber was a thick-wall car-
bon steel cylinder capped by two steel flanges with O-ring
seals. The 1.1 l chamber had an equal 114 mm diameter
and length. The chamber was well-insulated and wrapped
in electric heating elements to obtain initial temperatures
in the range from 298 K to 498 K. Two K-type thermocou-
ples were positioned on the cell exterior and inside chamber
to monitor the initial temperature. An extended-electrode
spark plug, located along the axis of the chamber and insu-
lated by heat shrink tubing, ensured the central spark.
2.2. Data acquisition system
The data acquisition system was a Labview-controlled
NI CB-68 LP card with two pressure transducers used
 P. Han et al. / Fuel 86 (2007) 585–596 587

for different ranges of initial pressure. A Flush Diaphragm
Pressure Transducer 7820 was used for 1 atmospheric pres-
sure experiments and an Omega PX800-2KSV pressure
transducer was used for experiments at elevated initial
pressures of up to 5 atm.
2.3. Experimental mixture
The experimental gases were methane, carbon dioxide,
nitrogen, carbon monoxide, hydrogen, and compressed
dry air. The experimental mixture was a stoichiometric
blend of three gas compositions: methane/air (V1), simu-
lated EGR (V2) and simulated reformer gas (V3) as shown
in Table 1. Fraction V1 consisted of 9.5% methane and
90.5% dry air, a stoichiometric methane/air mixture com-
position. The experimental EGR makeup, V2, consisted
of 18.5% CO2 and 81.5% N2 to simulate the exhaust gases.
This closely matches the molar mass and heat capacity of
the true exhaust gases from stoichiometric methane com-
bustion. The composition simulated by others only repre-
sented the dry exhaust gas and ignored the significant
water content of the real exhaust gas, whereas this compo-
sition was slightly different (14% CO2 and 86% N2 in [26] or
15% CO2 and 85% N2 in [27]). To maintain the stoichiom-
etric mixture, the reformer gas mixture, V3, was designed to
include 22.1% H2, 7.4% CO, and 70.5% air by volume.
Of course in all experiments, the contents of the cell com-
bined according to: V1 + V2 + V3 = 100% (by volume). The
experimental initial pressure ranged from 1 atm to 5 atm
and initial temperature varied from 298 K to 473 K. The
experimental initial conditions are displayed in Table 2.
Since 473 K is above the operating temperature range of
the pressure transducer Omega PX800-2KSV, the initial
temperature only ranged from 298 K to 423 K at 5 atm.
2.4. Experimental procedure
The mixture with desired components was prepared by
the partial pressure method in a 7 l stainless steel mixing
Table 1
Composition of experimental mixtures
V1 Methane–air 0.095V1 CH4 0.905V1 air
mixture
V2 EGR 0.185V2 CO2 0.815V2 N2
V3 Reformer gas 0.221V3 0.705V3 air
H2 + 0.074V3
CO
chamber at ambient temperature to ensure that each exper-
imental series had a consistent mixture. One experimental
series included experiments from 298 K to 473 K at a given
pressure with the same gas ratios. After the evacuated com-
bustion chamber was heated to the desired temperature,
the mixture was fed to the combustion chamber and
allowed to stabilize for 5–8 min before ignition. Wierzba
et al. [28–30] noted this short time had negligible effects
on flammability limits of hydrogen and no change on flam-
mability limits of either methane or carbon monoxide at
the initial temperature up to 473 K and ambient pressure.
Therefore, it is reliable to conclude that experimental
results were not changed by the short residence time. The
combustion chamber was evacuated during preheating to
avoid soot formation from the exhaust gases of the last
run, especially at high temperature and pressure. Goethals
et al. [31] tested the soot formation from the rich flamma-
bility limits of methane at elevated temperature and pres-
sure. Soot was found at 1 MPa and room temperature
and at 0.5 MPa and 473 K, respectively. Since the current
experimental initial conditions and equivalence ratio of
mixtures are far away from the above limits, soot forma-
tion was neglected at this study. The initial experimental
temperature was cautiously controlled to ±1 K. After the
ignition, the combustion pressure was measured by the
pressure transducer and collected at 5 kHz.
3. Calculation of burning velocity
3.1. Multi-zone thermodynamic equilibrium model
A multi-zone thermodynamic equilibrium model, used
previously [32–34], was used to calculate the laminar burn-
ing velocity from the pressure trace. The cylinder gas was
discretized into 1500 equal, spherical elements. Equilibrium
combustion and energy balance calculations were per-
formed on each zone. After the predicted pressure, unburnt
gas temperature, burnt gas temperature and relative flame
radius, etc. were interpolated with recorded experimental
pressure, burning velocity was obtained based on
dr
Su ¼ ð2Þ
dt
where dr is radial change of unburnt gas during the time
interval dt.
3.2. Calculation of burning velocity

In order to minimize the stretch and ignition effects, the

Table 2
Experimental initial conditions measured burning velocities from the largest flame radii
(45–57 mm) were fit by the following equation and then
Initial pressure 1 atm
Initial temperature 298 K 373 K 423 K 473 K extrapolated back to the initial experimental pressure to
Initial pressure 5 atm obtain the burning velocity [35]:
Initial temperature 298 K 373 K 423 K –  a  b
Initial temperature 298 K Tu P
Initial pressure 2 atm 3 atm 4 atm 5 atm
S u ¼ S u0 ð3Þ
T u0 P0
588
where Tu0 is reference unburnt gas temperature, 298 K; Tu
is unburnt gas temperature, K; P is pressure, atm; P0 is ref-
erence pressure, 1 atm; Su0 is laminar burning velocity at
reference temperature and pressure; a, b are constant val-
ues dependent on equivalence ratio and fuel properties.
Fig. 1 illustrates a typical calculated burning velocity
trace of a stoichiometric methane/air mixture as a function
of combustion pressure at 1 atm and 298 K. The solid line
indicates the curve fitted by Eq. (3) and the dotted line indi-
cates the extrapolation back to initial pressure, 1 atm.
These curve fits are initially accomplished using nominal
values of a and b (which is appropriate for the small tem-
perature and pressure extrapolations involved). More
appropriate values for a and b are later derived from burn-
ing velocities measured over series of experiments which
emphasize significant temperature and pressure ranges (as
described below).
Stretch rate has drawn considerable attention in the
study of laminar burning velocity [36–41]. The unstretched
laminar burning velocity may be derived from the stretched
laminar burning velocity and stretch rate. For example,
45 ± 2 cm/s was accepted as the burning velocity of stoichi-
ometric methane/air mixtures at 1 atm and 298 K in the
past [42,43]. However, Bosschaart and de Goey [44] dem-
onstrated that previously ignoring stretch led to over pre-
dictions. In order to eliminate the stretch effect, some
methods such as the counter flow method [45] were devel-
oped to unambiguously determine the unstretched laminar
burning velocity. However, Elia et al. [26] pointed out that
the correction of burning velocity from flame stretch is less
than 0.2 cm/s as the flame was close to their vessel wall (a
spherical vessel with a diameter of 15.24 cm) and 1 cm/s at
60
original data
50 curve fit line
extrapolated line
Burning velocity (cm/s)
40
30
20
100 150 200 250
Pressure (kPa)
Fig. 1. Calculation of burning velocities of methane/air mixtures at 298 K
and 1 atm.
P. Han et al. / Fuel 86 (2007) 585–596
the smaller flame radius. Similarly, Clarke et al. [27] used a
spherical combustion chamber with a diameter of 150 mm
in a micro-gravity environment and calculated burning
velocity for normalized flame radius from 0.49 to 0.93 cor-
responding to small stretch rate. They explained that the
flame stretch was sufficiently small after a normalized flame
radius of 0.66 and because of slow flame propagation of
methane/diluent mixtures they further demonstrated that
slow flame propagation decreased the stretch rate and
resulted in a lesser effect on burning velocity of methane/
diluent mixtures.
An ignition energy above the minimum required level
leads to a high apparent initial flame speed, but it has the
advantage of overcoming quenching effects. Bradley et al.
[46] showed that the enhancement of flame propagation
has been observed at the radii up to 10 mm with a very high
ignition energy of 1 J. In the current work, the burning
velocities from flame radius 45 mm (after stretch is negligi-
ble) to 57 mm (when the flame sphere contacts the wall)
were evaluated to obtain the burning velocity.
3.3. Nitric oxide model
Only nitric oxide was simulated for the purpose of this
research because the measurement difference between NO
and NOx was negligible in spark ignition engines which
burn near-stoichiometric mixture [47]. The NO equilibrium
concentration is strongly affected by flame temperature and
atomic oxygen concentration in mixtures. In this study, the
thermal NO equilibrium concentration was calculated from
the program STANJAN [48] simulating the constant-vol-
ume combustion for experimental initial temperature, pres-
sure and components.
4. Results and analysis
4.1. Laminar burning velocity
4.1.1. Effects of EGR
The data of burning velocities of methane/diluent mix-
tures at specific diluent compositions are scarce. Elia
et al. [26] measured the burning velocity of a methane/dil-
uent mixture in a spherical combustion chamber with a dil-
uent of 14% CO2 and 86% N2. Clarke et al. [27] determined
the burning velocity of methane/diluent mixture in a spher-
ical bomb at micro-gravity environment with a diluent of
15% CO2 and 85% N2. EGR diluent consisted of 18.5%
CO2 and 81.5% N2 in this study. Fig. 2 compares the burn-
ing velocities of methane/diluent mixtures at 298 K and
1 atm. The results agree well despite the minor difference
in diluent composition.
The thermodynamic effects of diluents (CO2 and N2) on
burning velocities of methane/air mixtures were analyzed
300 350 by Shrestha and Karim [49]. They also demonstrated that
the diluent reduces the effective heating value of the mix-
ture, which results in a lower flame temperature and conse-
quently decreases the burning velocity.
 P. Han et al. / Fuel 86 (2007) 585–596
Fig. 2. Burning velocity of methane/diluent mixture at 1 atm and 298 K.
Fig. 3 shows the measured burning velocity ratio against
the EGR percent. This ratio is the fractional reduction in
burning velocity due to the EGR for various initial temper-
atures. For example, the methane/20% EGR mixture only
has around 40% of the burning velocity of the methane/air
mixture. The initial temperature is effective in raising the
burning velocity and is seen to have a slightly more pro-
nounced effect at higher initial temperature. The exhaust
gas temperature in internal combustion engines can be
expected to be from 500 to 600 °C; in this range unburnt
Fig. 3. Burning velocity ratio as a function of EGR.
589
hydrocarbon emissions are limited and adequate tempera-
ture in the catalytic converter is maintained [9]. It is impor-
tant for this research to consider higher initial temperatures
because of the likelihood of this condition occurring with
EGR.
4.1.2. Effects of temperature
Fig. 4 compares the burning velocities of methane/air
mixtures at elevated initial temperature and 1 atm. Gu
et al. [38] and Sharma et al. [50] measured burning velocity
of methane/air mixture in a constant volume combustion
chamber at elevated initial temperature and pressure.
Mishra [51] investigated the initial temperature effect on
burning velocity of methane/air mixture by numerically
analyzing the flame structure and propagation. All of these
results agree well. It should be noted that the burning
velocities in this study, where stretch is insignificant at
the considered flame radii, agree extremely well with Gu’s
unstretched burning velocity.
Generally, increased initial temperature raises the burn-
ing velocity of fuels. A growing mass fraction of combus-
tion species, such as H2, CH3, H and CHO, resulting
from the elevated initial temperature, contributed to the
rising heat release rate. In addition, the elevated initial tem-
perature increased the total energy release. As a result, the
burning velocity was improved.
Fig. 5 illustrates the burning velocity ratio as a function
of initial temperature; the fractional rise in burning velocity
with increasing initial temperature. The observed increase
follows trends similar to predictions by Mishra [51].
Neglecting the methane/air mixtures, burning velocity
ratios of methane/EGR mixtures converge with a slight
Fig. 4. Burning velocity of methane/air mixture at elevated initial
temperature.
590 P. Han et al. / Fuel 86 (2007) 585–596

perature exponents as 1.68 and 1.857, respectively, despite

the similar bomb method. Iijima and Takeno [55] and Gu
et al. [38] showed similar temperature exponents, 1.6 and
1.612, respectively while Stone et al. [56] gave a lower tem-
perature exponent, 1.42, with a micro-gravity environment
measurement. Mishra [51] obtained a temperature expo-
nent of 1.575 with a chemical model. Liao et al. [57]
measured the laminar burning velocity of natural gas and
air mixture in a cubical chamber. The temperature expo-
nent for the stoichiometric mixture was determined as
1.58. In this study, the larger exponent of methane/EGR
mixtures indicates that initial temperature has more signifi-
cant impact on methane/EGR mixtures than methane/air
mixtures.

4.1.3. Effects of pressure

Fig. 5. Burning velocity as a function of initial temperature.
discrepancy at elevated initial temperature. This shows that
there is a consistent effect of temperature on the burning
velocity of methane/EGR mixtures regardless of the
EGR percent. The equation below was derived to fit the
burning velocity of methane/EGR mixtures at 1 atm and
elevated initial temperature, where Ti is initial temperature
in K and D is a volumetric fraction of EGR.
 2:0056
Ti
S u ¼ S u0 ð4aÞ
298
S u0 ¼ 229:7D2  157:6D þ 35:26
The high pressure restricts the flame propagation of
methane/air and methane/diluent mixtures and conse-
quently results in a low burning velocity. Fig. 6 illustrates
the burning velocities of stoichiometric methane/air mix-
tures and methane/15% EGR mixtures at initial pressures
up to 5 atm and 298 K. Obviously, the pressure has an
inversely proportional impact on burning velocity. At
5 atm, even a moderate 15% EGR cuts the burning velocity
to a low level. Furthermore, due to the unstable combus-
tion, a large amount of EGR is not applicable to meth-
ane-fueled engines despite the advantage of low NO
emission. The burning velocities in other studies are also
plotted in Fig. 6 for comparison. The burning velocities
of methane/15% EGR mixtures are in good agreement with
Elia’s [26] and Stone’s [56] data. Comparing the burning
velocities of stoichiometric methane/air mixtures with
ð4bÞ

Although this equation was derived from experimental

EGR fractions between 0.05 and 0.2, it is possible to extend
it to the full EGR range at 1 atm.
Burning velocities of stoichiometric methane/air mix-
tures at 1 atm were correlated well with a maximum error
of 0.5% using,
 1:653
Ti
S u ¼ 35:33 ð5Þ
298

where Ti is initial temperature in K.

The temperature exponent in the power law equation for
methane/air mixtures varied from different studies. An
early study by Andrews and Bradley [42] showed the expo-
nent as 2. Babkin and Kozachenko [52] and Rallis and
Garforth [53] both showed experimentally that the temper-
ature exponent was pressure dependent. Babkin and Koza-
chenko [52] also pointed out that the temperature exponent
increased with the lean mixture. Gülder [54] summarized
that the temperature exponent ranged from 1.37 to 2.33
with the various pressures and equivalence ratios. Sharma Fig. 6. Burning velocities of methane/air and methane/15% EGR
et al. [50] and Elia et al. [26] obtained quite different tem- mixtures at elevated pressure.
 P. Han et al. / Fuel 86 (2007) 585–596 591

those from Gu et al. [38], Sharma et al. [50], Elia et al. [26]
and Stone et al. [56], all results agree well with a maximum
of 2 cm/s difference including the higher burning velocities
of Sharma et al. and Stone et al. at 4 and 5 atm. Bradley
et al. [46] and Gu et al. [38] argued that the pressure above
atmospheric pressure masked the flame distortion and cel-
lularity which enhanced the burning velocity. The authors
believed that visual observation overcame the problems.
However, Gu’s recent results from photographic measure-
ment show good agreement with present results from pres-
sure measurement.
An empirical equation derived from the burning velocity
of stoichiometric methane/air mixtures at elevated pressure
and 298 K is
 0:37
Pi
S u ¼ 36:11 ð6Þ
P0
where Pi is initial pressure, atm and P0 is reference pres-
sure, 1 atm. The maximum error is 4%.
Different studies have given the various pressure expo-
nents in the power equation for methane/air mixture.
Andrews and Bradley [42] showed the pressure exponent Fig. 7. Burning velocity of methane/ air mixture at 5 atm.
as 0.5. Babkin and Kozachenko [52] gave a higher expo-
nent, 0.3. However, some studies investigated if the pres- the same pressure effect on temperature exponent and
sure exponent was pressure dependent. Rallis and Garforth attributed it to decrease in dissociation with increase in
[53] summarized that the pressure exponent was 0.51 at pressure but did not derive a relationship between the
3–10 atm pressure and 0.265 at 0.6–3 atm pressure. Gul- exponent and pressure.
der [54] found the pressure exponent to be 0.5 or 0.145. Note that Eqs. (4)–(7) all involve burning velocities fit-
Elia et al. [26] suggested the pressure exponent is 0.435. ted at 1 atm, 298 K. In this study, the best fit value at stan-
For stoichiometric methane/air mixture, Gu et al. [38] dard conditions varies from 35.3 cm/s to 36.1 cm/s
and Liao et al. [57] reached similar pressure exponents, depending on the conditions and range of values being fit.
0.374 and 0.398, respectively. Stone et al. [56] obtained
a larger pressure exponent, 0.297.
The burning velocity of methane/air mixtures at 5 atm 4.2. Effects of reformer gas
and elevated initial temperature is plotted in Fig. 7 and is
compared with burning velocity from other studies Hydrogen has a high burning velocity. Heimel [58] mea-
[50,53]. The following equation for burning velocity of stoi- sured the burning velocity of hydrogen/air mixtures at ele-
chiometric methane/air mixtures at elevated initial temper- vated temperature, and Iijima and Takeno [55] measured
ature and pressure was derived. that at elevated pressure. The burning velocities of stoichi-
 0:37  a ometric hydrogen/air mixture from above two studies are
Pi Ti plotted in Fig. 8. The reformer gas in this study consisted
S u ¼ 36:11
P0 298 ð7Þ of 22.1% H2, 7.4% CO and 70.5% air by volume to simulate
a ¼ 1:5365 þ 0:1165P i the ideal steam reforming products of methane. McLean
et al. [59] determined that the burning velocity with similar
where Pi is initial pressure, atm; P0 is reference pressure, constituents at 1 atm and 298 K was 156.7 cm/s, much
1 atm; Ti is initial temperature, K; a is the temperature higher than the burning velocity of methane/air mixture
exponent as a function of initial pressure. at the same conditions. Evidently, reformer gas has poten-
The initial temperature ranges from 298 K to 473 K and tial to enhance the combustion of methane/diluent mix-
initial pressure ranges from 1 atm to 5 atm. The experimen- tures by its high burning velocity.
tal initial temperature ranges from 298 K to 423 K at In the current work, the repeated experiments were run
5 atm, but it is reasonable to extrapolate the equation to at each diluent level. The percent of reformer gas was var-
473 K since the extrapolated results agree well with previ- ied at each level in order to identify the required amount to
ously published results at 473 K as shown in Fig. 7. The return the burning velocity to the value of undiluted meth-
maximum error is 5.4% and the other errors are less than ane/air. Table 3 displays the fractions of EGR, correspond-
3%. ing fractions of reformer gas and the ratios of fractions of
The temperature exponent is pressure dependent as reformer gas to EGR. Figs. 9 and 10 display plots of the
shown in Eq. (7). Babkin and Kozachenko [52] also found reformer gas effects on burning velocities of methane/
592 P. Han et al. / Fuel 86 (2007) 585–596

Fig. 8. Burning velocity of stoichiometric hydrogen/air mixture. Fig. 9. Reformer gas effects on burning velocity of methane/10% EGR
mixture at 1 atm.

EGR mixtures at 1 atm. Note that reformer gas raises the

burning velocity at the full range of initial temperatures. mixture at 5 atm. In other words, methane/40% EGR/
In other words, the percent of reformer gas is temperature 53% reformer gas mixture has the same burning velocity
independent, but dependent on pressure and percent of with stoichiometric methane/air mixture at 5 atm. There-
EGR. The ratio of reformer gas to EGR at high pressure fore, the reformer gas widens the flammability limits of
decreases, possibly due to the increase of the burning veloc- methane/EGR mixtures and broadens the tolerance of
ity of hydrogen/air mixtures with pressure. The burning EGR use in methane-fueled engines. The burning velocities
velocity of stoichiometric hydrogen/air mixture at 5 atm of methane/air mixtures and methane/40% EGR/53%
is about 2.4 times that at 1 atm from Fig. 8. The ratio of reformer gas mixtures at 5 atm and elevated initial temper-
fractions of reformer gas to EGR declines with EGR frac-
tion indicating the rising effect on burning velocity with
reformer gas caused by the increases of H atom and the
chain branching reaction O2 + H M O + OH [60].
It can be readily found from Fig. 6 that the methane/
15% EGR mixture is close to the flammability limit at
5 atm and 298 K. Hence, greater than 15% EGR under-
mines the stability of methane combustion at 5 atm. In
fact, the methane/30% EGR mixture could not be ignited
at 5 atm in the experiment. In order to take advantage of
the desirable fuel economy and low emissions of high
EGR, the reformer gas was used with methane/40% EGR
mixtures to achieve the target of undiluted burning veloc-
ity. After repeated experiments, it was found that 53%
reformer gas suits the demand for the methane/40% EGR

Table 3
EGR and required reformer gas fractions to retain the undiluted burning
velocity
Initial pressure 1 atm 5 atm
EGR dilution 0.05 0.1 0.15 0.2 0.4
RG required 0.11 0.19 0.28 0.34 0.53
RG/EGR 2.2 1.9 1.867 1.7 1.325
Fig. 10. Reformer gas effects on burning velocity of methane/20% EGR
Correlated RG 0.11 0.194 0.272 0.345 0.53
mixture at 1 atm.
 P. Han et al. / Fuel 86 (2007) 585–596
Fig. 11. Reformer gas effects on burning velocity of methane/40% EGR
mixture at 5 atm.
ature are compared with the burning velocities of methane/
air mixtures at 1 atm shown in Fig. 11.
In order to find a relationship between fractions of EGR
and reformer gas which produces the same burning veloc-
ity, several empirical equations were tried. The equation
 0:0885
Pi
RG ¼ expð0:8269 log D þ 0:2652Þ ð8Þ
P0
where D and RG are volumetric fractions of EGR and
reformer gas, respectively; Pi is initial pressure, atm; P0 is
1 atm, provided the best fit with a 3% maximum error.
The correlated fractions of reformer gas are also given in
Table 3.
4.3. Nitric oxide equilibrium concentration
It has been reported that diluent (CO2 and N2) decreases
the thermal enthalpy of the mixture and results in the
reduction of flame temperature [61]. Since flame tempera-
ture plays a decisive role in NO formation, EGR dramati-
cally decreases the NO concentration. Fig. 12 illustrates the
EGR effects on predicted NO equilibrium concentration at
1 atm.
The elevated initial temperature increases NO concen-
tration by increasing the flame temperature and decreasing
the peak pressure. Both changes on flame temperature and
peak pressure promote carbon dioxide dissociation and
therefore produce more oxygen resulting in greater NO
concentration.
Elevated pressure was observed to slightly decrease the
nitric oxide concentration. Drake and Richard showed
the same descending trend of NO equilibrium concentra-
593
Fig. 12. Calculated NO equilibrium concentration of methane/EGR
mixture at 1 atm.
tion in a stoichiometric methane/air mixture [62]. The rea-
sons are contributed to the relationship of peak
combustion pressure with initial pressure. The higher pres-
sure prohibits the carbon dioxide dissociation and results
in less oxygen in the combustion products, which leads to
a decreasing nitric oxide concentration.
This study has successfully introduced reformer gas to
methane/EGR mixtures to retain the burning velocity at
the undiluted level. Meanwhile, it is well known that H2
addition on methane/air mixture decreases the NO species
but CO addition increases the NO species [60]. However, it
is unknown if the reformer gas drastically damages the low
NO emission of methane/EGR mixtures. Two examples
are plotted in Fig. 13 to show the effects of reformer gas
on NO equilibrium concentration of methane/EGR mix-
tures. From this, it is reasonable to draw the conclusion
that the NO concentration of methane/EGR/reformer
gas mixtures is lower than that of methane/air mixtures
but higher than that of methane/EGR mixtures.
Fig. 14 shows the effects of 53% reformer gas on NO
equilibrium concentration of methane/40% EGR mixtures
at 5 atm and elevated initial temperature. The significant
advantage of large amount of EGR and EGR/reformer
gas mixture is easily seen from the figure. The methane/
40% EGR mixture has less than 4–7% of the NO emission
compared with the methane/air mixture. With an addi-
tional 53% reformer gas, the nitric oxide emission is still
less than 8–12% based on the NO emission of the meth-
ane/air mixture. The methane/40% EGR is out of the flam-
mability limit in the experiments, but with 53% reformer
gas addition, the mixture has the same burning velocity
as the methane/air mixture. Clearly, the methane/40%
EGR/53% reformer gas mixture has significant advantage.
594
Fig. 13. Calculated NO equilibrium concentration of methane/20% EGR
mixture with reformer gas addition.
Fig. 14. Calculated NO equilibrium concentration of methane/40% EGR
mixture with reformer gas addition at 5 atm.
In summary, reformer gas is especially effective for large
amounts of EGR to improve the combustion stability
and reduce nitric oxide emissions.
5. Conclusions
The effects of temperature, pressure, EGR and reformer
gas on the burning velocities of methane/air mixtures have
been shown, leading to the following conclusions:
P. Han et al. / Fuel 86 (2007) 585–596
1. Initial temperature has a large impact on the burning
velocity. An elevated initial temperature profoundly
increases the burning velocity of fuel/air mixtures.
2. The burning velocities of methane/air and methane/dil-
uent mixtures are decreased by elevated initial pressure,
but the burning velocities of hydrogen/air mixtures are
raised by elevated initial pressure.
3. Diluent, or EGR, decreases burning velocities of meth-
ane/air mixtures. At 5 atm, the methane/15% EGR mix-
ture is close to the flammability limit.
4. Reformer gas shows great potential for extending EGR
applicability by mitigating the reduced flame speeds
associated with EGR. Thus, sufficient fuel reforming
was found to maintain the burning velocity of meth-
ane/EGR mixtures at undiluted level. The required frac-
tion of reformer gas is temperature independent but
depends on the rate of EGR and on the initial pressure.
A correlation relationship between fractions of reformer
gas and EGR was derived.
5. A series of empirical power equations of the effects of
temperature, pressure and EGR on burning velocity of
methane/air mixtures were derived. All equations fit
the data of burning velocities reasonably well.
6. It was found that EGR dramatically reduces predicted
NO concentration, especially at high pressure. The
amount of reformer gas required to raise the burning
velocity to an undiluted level increases NO emissions
somewhat, but the predicted NO concentration is lower
than that of methane/air mixtures, especially at high
pressure. In summary, reformer gas has the potential
to improve the combustion and reduce the oxides of
nitrogen emissions of methane/air mixtures.
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