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Fuel 86 (2007) 585–596

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


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.

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

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
586 P. Han et al. / Fuel 86 (2007) 585–596

hydrogen’s advantages. Therefore, on-board fuel reform- and efficiency. Overall, when considering both NOx emis-
ing that converts hydrocarbon fuel to reformer gas, such sion and torque output, stoichiometric mixtures with
as hydrogen and carbon monoxide, has been developed EGR produced nearly 30% more torque than lean-burn
to meet the demands. Tully and Heywood found that refor- mixtures and low NOx emission (<10 ppm) in a hydro-
mer gas raised the peak net indicated fuel conversion effi- gen-fueled engine [18]. It is for this reason that stoichiom-
ciency 12% while cutting NOx emissions 94% at the peak etric mixtures were used in the present work.
efficiency point compared to data obtained from a gasoline Houseman and Cerini studied the possibility of onboard
engine operating stoichiometrically [12]. In summary, the steam reforming of gasoline or methanol to generate
reformer gas is able to potentially broaden the tolerance hydrogen for automobiles and demonstrated that it is tech-
of EGR and maintain combustion stability. nically feasible [19]. A catalyst, such as Ni-YSZ, is strongly
The laminar burning velocity is a fundamental parameter recommended to reduce the reaction temperature of meth-
required to understand the combustion process and flame ane steam reforming [20,21]. Chen et al. produced a large
propagation. It is also a necessary input to model turbulent volume of hydrogen at a relatively low temperature by
combustion and pollutant formation. Precise values of lam- using an improved novel membrane reformer to stimulate
inar burning velocities are useful for practical applications the steam reforming of methane [22]. The review by Jamal
on internal combustion engines, which operate at pressures and Wyszynski [23] found that steam reforming generated
varying from 5 atm to 60 atm and unburnt gas temperature the maximum quantity of hydrogen compared to other
ranging from 500 K to 1100 K [13]. In other studies, the methods of hydrogen production, and did not involve
burning velocities and flammability limits of n-butane and nitrogen. Despite using an exothermic reaction, another
iso-butane with reformer gas addition were analyzed at method of hydrogen production, partial oxidation, pro-
room temperature [14]. In addition, the effects of reformer duced less hydrogen than steam reforming. In particular,
gas on engine performance and characteristics at near dilu- partial oxidation of gasoline yields one quarter hydrogen,
ent limit and lean mixture were also investigated [12,15]. one quarter carbon monoxide, and one half nitrogen
However, all of these studies were focused on gasoline or [12,15]. Additional CO was found to be slightly effective
partial oxidation reaction, and data for burning velocities in improving combustion efficiency, emissions and stability
of methane/EGR/reformer gas mixtures is scarce, especially [12]. Steam reforming has relatively low costs, compara-
at elevated temperature and pressure to simulate real engine tively high efficiency, and it is able to ideally produce the
operation. The burning velocity at elevated temperature maximum amount of hydrogen, 75% [24]. Thus, steam
and pressure is more useful in understanding the effects of reforming’s hydrogen-rich products were used for these
diluents and reformer gas. Furthermore, an interesting experiments. The reformer gas was simulated by a mixture
question remains whether the methane/EGR/reformer gas of H2 and CO with volumetric ratio of 3:1, which corre-
mixture loses the potential of low NO emission while main- sponded to the ideal products of steam reforming of meth-
taining the undiluted burning velocity. ane as shown in
Methane, a major component of natural gas, was used in
CH4 + H2 O = CO + 3H2 ð1Þ
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/ 2. Experimental apparatus and method
hydrogen ratio of methane provide the natural gas engine
fundamental emission advantages [8]. However, the natural 2.1. Combustion chamber
gas engine has undesirably high NO emissions [9] despite
thorough development [16,17]. Thus, EGR is essential for A combustion chamber designed by Checkel et al. [25]
a methane-fueled engine. Unfortunately, compared with employing a preheated high-pressure cylinder with central
gasoline and methanol-fueled engines, the methane-fueled spark ignition was used. The chamber was a thick-wall car-
engine’s EGR tolerance is the poorest [7]. Specifically, a nat- bon steel cylinder capped by two steel flanges with O-ring
ural gas engine running at IMEP of 2 atm and 2000 rpm has seals. The 1.1 l chamber had an equal 114 mm diameter
a maximum EGR tolerance of 8% [9]. Therefore, reformer and length. The chamber was well-insulated and wrapped
gas is necessary to broaden the methane-fueled engine’s in electric heating elements to obtain initial temperatures
EGR tolerance and improve its combustion stability. in the range from 298 K to 498 K. Two K-type thermocou-
This study focuses on the stoichiometric mixtures used ples were positioned on the cell exterior and inside chamber
with 3-way catalyst systems, though engines operating with to monitor the initial temperature. An extended-electrode
lean mixture have greater efficiency [12], lower flame tem- spark plug, located along the axis of the chamber and insu-
perature and reduced NOx emission. Their lower flame lated by heat shrink tubing, ensured the central spark.
temperature leads to low chemical heat release rates and
thus the loss of maximum power. Stoichiometric mixtures 2.2. Data acquisition system
are comparatively worse than lean mixtures in NOx emis-
sions, but 3-way catalytic converters require the exhaust The data acquisition system was a Labview-controlled
gas of stoichiometric combustion for the best effectiveness 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 chamber at ambient temperature to ensure that each exper-
Pressure Transducer 7820 was used for 1 atmospheric pres- imental series had a consistent mixture. One experimental
sure experiments and an Omega PX800-2KSV pressure series included experiments from 298 K to 473 K at a given
transducer was used for experiments at elevated initial pressure with the same gas ratios. After the evacuated com-
pressures of up to 5 atm. bustion chamber was heated to the desired temperature,
the mixture was fed to the combustion chamber and
2.3. Experimental mixture allowed to stabilize for 5–8 min before ignition. Wierzba
et al. [28–30] noted this short time had negligible effects
The experimental gases were methane, carbon dioxide, on flammability limits of hydrogen and no change on flam-
nitrogen, carbon monoxide, hydrogen, and compressed mability limits of either methane or carbon monoxide at
dry air. The experimental mixture was a stoichiometric the initial temperature up to 473 K and ambient pressure.
blend of three gas compositions: methane/air (V1), simu- Therefore, it is reliable to conclude that experimental
lated EGR (V2) and simulated reformer gas (V3) as shown results were not changed by the short residence time. The
in Table 1. Fraction V1 consisted of 9.5% methane and combustion chamber was evacuated during preheating to
90.5% dry air, a stoichiometric methane/air mixture com- avoid soot formation from the exhaust gases of the last
position. The experimental EGR makeup, V2, consisted run, especially at high temperature and pressure. Goethals
of 18.5% CO2 and 81.5% N2 to simulate the exhaust gases. et al. [31] tested the soot formation from the rich flamma-
This closely matches the molar mass and heat capacity of bility limits of methane at elevated temperature and pres-
the true exhaust gases from stoichiometric methane com- sure. Soot was found at 1 MPa and room temperature
bustion. The composition simulated by others only repre- and at 0.5 MPa and 473 K, respectively. Since the current
sented the dry exhaust gas and ignored the significant experimental initial conditions and equivalence ratio of
water content of the real exhaust gas, whereas this compo- mixtures are far away from the above limits, soot forma-
sition was slightly different (14% CO2 and 86% N2 in [26] or tion was neglected at this study. The initial experimental
15% CO2 and 85% N2 in [27]). To maintain the stoichiom- temperature was cautiously controlled to ±1 K. After the
etric mixture, the reformer gas mixture, V3, was designed to ignition, the combustion pressure was measured by the
include 22.1% H2, 7.4% CO, and 70.5% air by volume. pressure transducer and collected at 5 kHz.
Of course in all experiments, the contents of the cell com-
bined according to: V1 + V2 + V3 = 100% (by volume). The 3. Calculation of burning velocity
experimental initial pressure ranged from 1 atm to 5 atm
and initial temperature varied from 298 K to 473 K. The 3.1. Multi-zone thermodynamic equilibrium model
experimental initial conditions are displayed in Table 2.
Since 473 K is above the operating temperature range of A multi-zone thermodynamic equilibrium model, used
the pressure transducer Omega PX800-2KSV, the initial previously [32–34], was used to calculate the laminar burn-
temperature only ranged from 298 K to 423 K at 5 atm. ing velocity from the pressure trace. The cylinder gas was
discretized into 1500 equal, spherical elements. Equilibrium
2.4. Experimental procedure combustion and energy balance calculations were per-
formed on each zone. After the predicted pressure, unburnt
The mixture with desired components was prepared by gas temperature, burnt gas temperature and relative flame
the partial pressure method in a 7 l stainless steel mixing radius, etc. were interpolated with recorded experimental
pressure, burning velocity was obtained based on
Table 1
Composition of experimental mixtures Su ¼ ð2Þ
V1 Methane–air 0.095V1 CH4 0.905V1 air
mixture where dr is radial change of unburnt gas during the time
V2 EGR 0.185V2 CO2 0.815V2 N2
interval dt.
V3 Reformer gas 0.221V3 0.705V3 air
H2 + 0.074V3
CO 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 P. Han et al. / Fuel 86 (2007) 585–596

where Tu0 is reference unburnt gas temperature, 298 K; Tu the smaller flame radius. Similarly, Clarke et al. [27] used a
is unburnt gas temperature, K; P is pressure, atm; P0 is ref- spherical combustion chamber with a diameter of 150 mm
erence pressure, 1 atm; Su0 is laminar burning velocity at in a micro-gravity environment and calculated burning
reference temperature and pressure; a, b are constant val- velocity for normalized flame radius from 0.49 to 0.93 cor-
ues dependent on equivalence ratio and fuel properties. responding to small stretch rate. They explained that the
Fig. 1 illustrates a typical calculated burning velocity flame stretch was sufficiently small after a normalized flame
trace of a stoichiometric methane/air mixture as a function radius of 0.66 and because of slow flame propagation of
of combustion pressure at 1 atm and 298 K. The solid line methane/diluent mixtures they further demonstrated that
indicates the curve fitted by Eq. (3) and the dotted line indi- slow flame propagation decreased the stretch rate and
cates the extrapolation back to initial pressure, 1 atm. resulted in a lesser effect on burning velocity of methane/
These curve fits are initially accomplished using nominal diluent mixtures.
values of a and b (which is appropriate for the small tem- An ignition energy above the minimum required level
perature and pressure extrapolations involved). More leads to a high apparent initial flame speed, but it has the
appropriate values for a and b are later derived from burn- advantage of overcoming quenching effects. Bradley et al.
ing velocities measured over series of experiments which [46] showed that the enhancement of flame propagation
emphasize significant temperature and pressure ranges (as has been observed at the radii up to 10 mm with a very high
described below). ignition energy of 1 J. In the current work, the burning
Stretch rate has drawn considerable attention in the velocities from flame radius 45 mm (after stretch is negligi-
study of laminar burning velocity [36–41]. The unstretched ble) to 57 mm (when the flame sphere contacts the wall)
laminar burning velocity may be derived from the stretched were evaluated to obtain the burning velocity.
laminar burning velocity and stretch rate. For example,
45 ± 2 cm/s was accepted as the burning velocity of stoichi- 3.3. Nitric oxide model
ometric methane/air mixtures at 1 atm and 298 K in the
past [42,43]. However, Bosschaart and de Goey [44] dem- Only nitric oxide was simulated for the purpose of this
onstrated that previously ignoring stretch led to over pre- research because the measurement difference between NO
dictions. In order to eliminate the stretch effect, some and NOx was negligible in spark ignition engines which
methods such as the counter flow method [45] were devel- burn near-stoichiometric mixture [47]. The NO equilibrium
oped to unambiguously determine the unstretched laminar concentration is strongly affected by flame temperature and
burning velocity. However, Elia et al. [26] pointed out that atomic oxygen concentration in mixtures. In this study, the
the correction of burning velocity from flame stretch is less thermal NO equilibrium concentration was calculated from
than 0.2 cm/s as the flame was close to their vessel wall (a the program STANJAN [48] simulating the constant-vol-
spherical vessel with a diameter of 15.24 cm) and 1 cm/s at ume combustion for experimental initial temperature, pres-
sure and components.

60 4. Results and analysis

4.1. Laminar burning velocity

original data 4.1.1. Effects of EGR

50 curve fit line
extrapolated line
The data of burning velocities of methane/diluent mix-
tures at specific diluent compositions are scarce. Elia
Burning velocity (cm/s)

et al. [26] measured the burning velocity of a methane/dil-

uent mixture in a spherical combustion chamber with a dil-
40 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-
30 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
100 150 200 250 300 350 by Shrestha and Karim [49]. They also demonstrated that
Pressure (kPa) the diluent reduces the effective heating value of the mix-
Fig. 1. Calculation of burning velocities of methane/air mixtures at 298 K ture, which results in a lower flame temperature and conse-
and 1 atm. quently decreases the burning velocity.
P. Han et al. / Fuel 86 (2007) 585–596 589

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

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-
Fig. 2. Burning velocity of methane/diluent mixture at 1 atm and 298 K.
tion species, such as H2, CH3, H and CHO, resulting
from the elevated initial temperature, contributed to the
Fig. 3 shows the measured burning velocity ratio against rising heat release rate. In addition, the elevated initial tem-
the EGR percent. This ratio is the fractional reduction in perature increased the total energy release. As a result, the
burning velocity due to the EGR for various initial temper- burning velocity was improved.
atures. For example, the methane/20% EGR mixture only Fig. 5 illustrates the burning velocity ratio as a function
has around 40% of the burning velocity of the methane/air of initial temperature; the fractional rise in burning velocity
mixture. The initial temperature is effective in raising the with increasing initial temperature. The observed increase
burning velocity and is seen to have a slightly more pro- follows trends similar to predictions by Mishra [51].
nounced effect at higher initial temperature. The exhaust Neglecting the methane/air mixtures, burning velocity
gas temperature in internal combustion engines can be ratios of methane/EGR mixtures converge with a slight
expected to be from 500 to 600 °C; in this range unburnt

Fig. 4. Burning velocity of methane/air mixture at elevated initial

Fig. 3. Burning velocity ratio as a function of EGR. 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

4.1.3. Effects of pressure

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-
Fig. 5. Burning velocity as a function of initial temperature. 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
discrepancy at elevated initial temperature. This shows that 5 atm, even a moderate 15% EGR cuts the burning velocity
there is a consistent effect of temperature on the burning to a low level. Furthermore, due to the unstable combus-
velocity of methane/EGR mixtures regardless of the tion, a large amount of EGR is not applicable to meth-
EGR percent. The equation below was derived to fit the ane-fueled engines despite the advantage of low NO
burning velocity of methane/EGR mixtures at 1 atm and emission. The burning velocities in other studies are also
elevated initial temperature, where Ti is initial temperature plotted in Fig. 6 for comparison. The burning velocities
in K and D is a volumetric fraction of EGR. of methane/15% EGR mixtures are in good agreement with
 2:0056 Elia’s [26] and Stone’s [56] data. Comparing the burning
S u ¼ S u0 ð4aÞ velocities of stoichiometric methane/air mixtures with
S u0 ¼ 229:7D2  157:6D þ 35:26 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,
S u ¼ 35:33 ð5Þ

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
S u ¼ 36:11 ð6Þ
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
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) 585–596 593

Fig. 12. Calculated NO equilibrium concentration of methane/EGR

Fig. 11. Reformer gas effects on burning velocity of methane/40% EGR mixture at 1 atm.
mixture at 5 atm.

ature are compared with the burning velocities of methane/ tion in a stoichiometric methane/air mixture [62]. The rea-
air mixtures at 1 atm shown in Fig. 11. sons are contributed to the relationship of peak
In order to find a relationship between fractions of EGR combustion pressure with initial pressure. The higher pres-
and reformer gas which produces the same burning veloc- sure prohibits the carbon dioxide dissociation and results
ity, several empirical equations were tried. The equation in less oxygen in the combustion products, which leads to
 0:0885 a decreasing nitric oxide concentration.
Pi This study has successfully introduced reformer gas to
RG ¼ expð0:8269 log D þ 0:2652Þ ð8Þ methane/EGR mixtures to retain the burning velocity at
the undiluted level. Meanwhile, it is well known that H2
where D and RG are volumetric fractions of EGR and addition on methane/air mixture decreases the NO species
reformer gas, respectively; Pi is initial pressure, atm; P0 is but CO addition increases the NO species [60]. However, it
1 atm, provided the best fit with a 3% maximum error. is unknown if the reformer gas drastically damages the low
The correlated fractions of reformer gas are also given in NO emission of methane/EGR mixtures. Two examples
Table 3. are plotted in Fig. 13 to show the effects of reformer gas
on NO equilibrium concentration of methane/EGR mix-
4.3. Nitric oxide equilibrium concentration tures. From this, it is reasonable to draw the conclusion
that the NO concentration of methane/EGR/reformer
It has been reported that diluent (CO2 and N2) decreases gas mixtures is lower than that of methane/air mixtures
the thermal enthalpy of the mixture and results in the but higher than that of methane/EGR mixtures.
reduction of flame temperature [61]. Since flame tempera- Fig. 14 shows the effects of 53% reformer gas on NO
ture plays a decisive role in NO formation, EGR dramati- equilibrium concentration of methane/40% EGR mixtures
cally decreases the NO concentration. Fig. 12 illustrates the at 5 atm and elevated initial temperature. The significant
EGR effects on predicted NO equilibrium concentration at advantage of large amount of EGR and EGR/reformer
1 atm. gas mixture is easily seen from the figure. The methane/
The elevated initial temperature increases NO concen- 40% EGR mixture has less than 4–7% of the NO emission
tration by increasing the flame temperature and decreasing compared with the methane/air mixture. With an addi-
the peak pressure. Both changes on flame temperature and tional 53% reformer gas, the nitric oxide emission is still
peak pressure promote carbon dioxide dissociation and less than 8–12% based on the NO emission of the meth-
therefore produce more oxygen resulting in greater NO ane/air mixture. The methane/40% EGR is out of the flam-
concentration. mability limit in the experiments, but with 53% reformer
Elevated pressure was observed to slightly decrease the gas addition, the mixture has the same burning velocity
nitric oxide concentration. Drake and Richard showed as the methane/air mixture. Clearly, the methane/40%
the same descending trend of NO equilibrium concentra- EGR/53% reformer gas mixture has significant advantage.
594 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
Fig. 13. Calculated NO equilibrium concentration of methane/20% EGR
mixture with reformer gas addition.
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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