Fuel 343 (2023) 127991

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Experimental and numerical study on the ignition delay times of methane/

propane mixtures diluted in carbon dioxide
Wenxiang Xia , Chun Zou *, Yi Yuan , Rui Fu , Jiacheng Liu , Chao Peng
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Pressurized oxy-fuel combustion has gained great interest owing to its low emission and high efficiency. Methane
Oxy-fuel combustion and propane are important composition of natural gas, which is a clean fossil fuel and widely utilized for
CH4/C3H8 mixture combustion applications including gas turbines. In this work, the auto-ignition properties of CH4/C3H8 mixtures
Ignition delay time
in ratios from 90/10% to 70/30% diluted in CO2 were measured at pressures of 1.75 and 10 atm; equivalence
Chemical kinetics
ratios of 0.5, 1.0, and 2.0; and temperatures in the range of 1240–1520 K in a shock tube. Four key reactions in
the Oxymech 2.0 model were updated and the modified model shows reasonable performance in both the
ignition delay time and the laminar flame speed predictions in O2/N2 and O2/CO2 atmospheres. Two kinetic
models (NUIG 1.0 and AramcoMech 3.0) were evaluated by present data and the laminar flame speed from the
literature. The results of the experiment and calculation show that the addition of propane promotes the ignition
significantly in the C3H8 proportion range from 0 to 30% in both cases of CO2 and N2, but has slight effects on the
ignition with the C3H8 proportion more than 30%. The effects of CO2 on the promoting effects of C3H8 addition
are slight. The ignition delay times increase with the equivalence ratio at 1.75 atm but no statistical difference is
observed between the measured data of different equivalence ratios at 10 atm. The influence of C3H8 addition
and the equivalence ratio on the ignition delay of CH4/C3H8 mixtures was also analyzed in detail.

1. Introduction
The emission of carbon dioxide from the combustion of fossil fuels, as
a cause of global warming, has gained great interest in recent years
[1–3]. Oxy-fuel combustion, in which the combustion occurs in the O2/
CO2 atmosphere, is a promising carbon capture technology due to the
high CO2 concentration product gas for easier carbon capture [4,5]. The
direct semi-closed oxy-combustion cycle using natural gas, the Allam
cycle, is capable of capturing CO2 with a net efficiency up to 59% LHV
[6,7]. Therefore, the pressurized oxy-fuel combustion of natural gas has
attracted much attention.
Natural gas is primarily composed of methane with some heavier
alkanes ranging from ethane to heptane depending on its origin,
extraction, and transport processes [8]. Although the fractional contri­
bution of propane to the composition of conventional natural gas is
small, the contribution of propane to the combustion of natural gas
cannot be ignored. There are various experimental and kinetic modeling
studies for ignition delay time (IDT) [9–13] and laminar flame speed
(LFS) [14–17] of a wide range of methane/propane mixtures diluted in
Ar or N2.
Petersen et al. [10] measured the IDTs of fuel mixtures consisting of
CH4/C3H8 in ratios ranging from 90%/10% to 60%/40% at gas turbine
pressures by shock tube and found that increasing the blend ratios of
propane from 10% to 30% can decrease the IDTs. They also proposed a
CH4/C3H8 oxidation mechanism to simulate the experimental results
and mentioned that the reactions involving CH3O, CH3O2, and CH3 +
O2/HO2 were important in reproducing the correct kinetic behavior.
Then Healy et al. [11] extended the experiments to intermediate and low
temperature conditions using a rapid compression machine and updated
the kinetic model of CH4/C3H8 [10]. The model reproduced correctly
the ignition at conditions of various equivalence ratios and pressures.
Recently, El-Sabor Mohamed et al. [18] measured the IDTs of natural gas
mixtures comprising C1-C7 n-alkanes in air using a rapid compression
machine at gas turbine operating conditions and developed a compre­
hensive chemical kinetic model (NUIG 1.0), which can successfully
predict the experiments. Moreover, Lowry et al. [14] measured the LFSs
of 80 %CH4/20 %C3H8 mixtures in air at 1 and 5 atm using a constant-
volume vessel. Then Nilsson et al. [15] investigated the effects of

* Corresponding author.
E-mail address: zouchun@hust.edu.cn (C. Zou).

https://doi.org/10.1016/j.fuel.2023.127991
Received 27 July 2022; Received in revised form 12 February 2023; Accepted 24 February 2023
Available online 3 March 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
W. Xia et al. Fuel 343 (2023) 127991

hydrogen addition on the LFSs of 80 %CH4/20 %C3H8 mixtures and
pointed out that the Aramco 1.3 model [19] slightly over-predicted the
experimental results.
For the oxy-fuel combustion atmospheres, Hargis and Petersen [20]
measured the IDTs of CH4 diluted in 75 %CO2 in shock tubes and pointed
out that CH3 + H (+M) ⇔ CH4 (+M) and HCO + M ⇔ H + CO + M were
significant third-body reactions for the CH4 ignition at high tempera­
ture, while 2CH3 (+M) ⇔ C2H6 (+M) was significant at low temperature.
In our previous study [21–23], the IDTs of CH4, C2H6, and C3H8 diluted
in CO2 were measured and a kinetic model named Oxymech 2.0 was
developed, which was validated by experimental IDTs and LFSs for C1-
C3 alkanes in oxy-fuel and air combustion over a wide range of pressure.
To our knowledge, the IDTs of CH4/C3H8 mixtures in oxy-fuel com­
bustion are still lacking, and Oxymech 2.0 also needs validation by the
IDTs of CH4/C3H8 mixtures.
CO2 is not inert in oxy-fuel combustion, and the reaction rates of
third-body reactions in O2/CO2 atmospheres are enhanced due to the
chaperon effects of CO2. Liu et al. [21] found that the chemical effects of
CO2 suppress the ignition at lower temperature mainly due to the
chaperon effects of 2CH3 (+M) ⇔ C2H6 (+M) while promoting the
ignition of CH4 at higher temperature mainly due to the chaperon effects
of HCO + M ⇔ H + CO + M at 0.8 and 1.75 atm. The kinetic analysis by
Xia et al. [23] indicated that C3H8 (+M) ⇔ C2H5 + CH3 (+M) plays an
important role in third-body reactions for the C3H8 ignition. Obviously,
the influence of CO2 on CH4/C3H8 ignition needs further investigation.
In this study, the IDTs of CH4/C3H8 mixtures with ratios ranging
from 90%/10% to 70%/30% diluted in CO2 were measured at pressures
of 1.75 and 10 atm; equivalence ratios of 0.5, 1.0, and 2.0; and tem­
peratures in the range of 1240–1520 K in a shock tube. The modified
Oxymech 2.0 model by updating four key reactions was validated by the
IDTs and LFSs of CH4/C3H8 mixtures in both oxy-fuel and air combus­
tion. Two kinetic models (NUIG 1.0, and AramcoMech 3.0) were eval­
uated using the experimental IDTs and the LFSs from the literature. The
effects of the CH4/C3H8 ratio and the equivalence ratio on the IDTs of
CH4/C3H8 mixtures were also analyzed in detail.
2. Experiments
As shown in Fig. 1, the IDT is defined as the time interval between the
arrival of the reflected shocks and the onset of ignition, which is
determined by extrapolating the maximum slope of the normalized OH*
emission linearly back to the zero baseline. Moreover, the shock bifur­
cation due to the large addition of CO2 could result in the difficult
determination of the main reflected wave arriving. Laich et al. [24] and
Ninnemann et al. [25] have studied the shock bifurcation under CO2
dilution in detail. In this study, the arrival time of the reflected shock, tA ,
was determined using the empirical formula proposed by Petersen and
Hanson [26]:
D
tA = ti + + ΔtAO (1)
2VR
where ti denotes the time when the initial pressure rises,VR denotes the
velocity of the reflected shock, and D denotes the diameter of the
pressure transducer (Kistler 603B1). The ΔtAO can be expressed as:
(2)
0.57 − 7.1 0.66
ΔtAO (μs) = 4.6M γ 2 MS
where M denotes the molecular weight of the mixture, γ2 denotes the
specific heat ratio upstream of the bifurcation, and Ms denotes the Mach
number of the incident shocks. The temperature (T5) and pressure (P5)
behind the reflected shock waves were calculated by the chemical
equilibrium program, Gaseq [27]. The uncertainty in T5 was estimated
within ± 24 K, and the total uncertainty in the IDT measurements was
within 20%. A detailed analysis of the uncertainty can be obtained in the
Supplementary Material.
2.2. Experimental facilities and methods validation
In our previous work [21], the IDTs of CH4 in O2/CO2 atmosphere
were measured and compared with those from Hargis and Petersen [20]
at the equivalence ratio of 0.5 and the pressure of 1.75 atm and our data
conform fairly well to the results of Hargis and Peterson. In this study,
the IDTs of the CH4/C3H8 mixture in O2/N2 atmosphere were measured
and compared with those from the Petersen et al. [10] at the equivalence
ratio of 0.5 and the pressure of approximately 10 atm As shown in Fig. 2,

2.1. Facilities and methods

In this study, the ignition delay time measurements of CH4/C3H8

mixtures under O2/CO2 atmospheres were conducted in a shock tube,
with 4 m driver section, 8 m driven section, and an inner diameter of 0.1
m, as reported in our previous work in detail [21]. The tested conditions
are listed in Table 1. The purities of two fuels were 99.99% while the
purities of oxygen and dilution gases were all 99.999%. All the mixtures
required resting in a 300 L mixing tank for more than 12 h while pre­
paring. The mixing tank and the shock tube were evacuated to less than
0.1 Pa before operation. Five piezoelectric pressure transducers (PCB
111A24) were placed alongside the shock tube at intervals of 20 cm to
record the incident shock velocity. The pressure trace was captured
using a piezoelectric pressure transducer (Kistler 603B1) placed 2 cm
upstream the endwall, while a photomultiplier with a band pass filter of
307 ± 10 nm was placed 2 cm upstream the endwall to monitor the OH*
Fig. 1. Typical signals of the ignition delay time measurement for mix-1 at T =
emission. 1361 K and P = 10.2 atm.

Table 1
Composition of the experimental mixtures and test conditions.
Mixture CH4 C3H8 O2 CO2 N2 CH4/C3H8 Φ Pressure (atm)

Mix-1 3.93% 0.44% 20.09% 75.54% 0 9/1 0.5 1.75, 10

Mix-2 3.11% 0.78% 20.19% 75.92% 0 8/2 0.5 1.75, 10
Mix-3 2.45% 1.05% 20.27% 76.23% 0 7/3 0.5 1.75, 10
Mix-4 4.73% 2.03% 19.59% 73.66% 0 7/3 1.0 1.75, 10
Mix-5 8.86% 3.80% 18.35% 69.00% 0 7/3 2.0 1.75, 10
Mix-6 3.93% 0.44% 20.09% 0 75.54% 9/1 0.5 10

2
W. Xia et al. Fuel 343 (2023) 127991

hydrocarbon kinetic model and is widely utilized. These kinetic models

are evaluated by the experimental data in this study. The closed ho­
mogeneous batch reactor in the CHEMKIN-PRO software [33] was
adopted for the numerical calculation of IDTs. A pressure rise about
16%/ms owing to non-ideal effects appeared from 1100 μs behind the
reflected shock wave, as shown Fig. S1 in the supplemental material.
Considering the relatively short IDT, the pressure rise resulting from
non-ideal effect was considered negligible during simulation [34,35],
thus the constant U-V assumption was adopted without modification.
The calculated IDT is defined as the time interval between zero and the
moment of the maximum rate of temperature rise (max dT/dt).

4. Results and discussion

4.1. Model evaluation

Fig. 2. Comparison between the experimental data in this work and those from
Petersen et al. [10].
the measured data of the present work are consistent with the literature
data. These confirm the reliability of present facilities and methods for
the IDT measurement. The measured data are provided in the supple­
mental material.
3. Modeling
The Oxymech 2.0 model proposed in our previous study [23] per­
forms good agreement with the IDT data of CH4/C3H8 mixtures but over-
predicted most of the LFS data in fuel-rich conditions, as discussed in
next section. To improve the performance of Oxymech 2.0 on LFS pre­
dictions, four reactions were updated, which show high sensitivity to
LFS but not sensitive to IDT, as listed in Table 2. Baulch et al. [28]
provided the preferred values of the kinetic data of CH4 + H ⇔ CH3 + H2
(R43) based on the previous investigations. Jasper et al. [29] calculated
the rate coefficients of the pressure-dependent reaction CH3 + OH ⇔
CH2OH + H (R94) and only the low pressure limit chemical activation
rate constant expression was adopted in Oxymech 2.0. It is necessary to
apply the completed rate coefficients for different pressures. The rate
constants of C2H4 + H (+M) ⇔ C2H5 (+M) (R207) in AramcoMech 3.0
sourced from Miller and Klippenstein [30] were also adopted. The re­
action C2H3 + H ⇔ C2H2 + H2 (R300) can affect the LFSs of methane/
propane mixtures significantly and was also updated using the results
adopted in AramcoMech 3.0 [31].
Moreover, the NUIG 1.0 model [18] was developed with updated
reaction rates based on recent theoretical and experimental studies
together with the heptane mechanism developed by Zhang et al. [32]
and showed excellent agreement with the IDT measurements for C1-C7
n-alkanes. The AramcoMech 3.0 [31] model is a representative
Table 2
Key elementary reactions updated in the present studya.
Number Reaction A b Eα
Fig. 3 displays the measured IDT data for different CH4/C3H8 mix­
tures diluted in CO2 with different equivalence ratios at 1.75 atm and 10
atm and the simulated IDTs using the unmodified and modified Oxy­
mech 2.0, NUIG 1.0, and AramcoMech 3.0. As shown in Fig. 3, NUIG 1.0
and AramcoMech 3.0 over-predict nearly all of the IDTs. Oxymech 2.0
and the modified model show reasonable performance in most of the IDT
predictions. The absolute relative error (ARE) was introduced to eval­
uate the four models quantitatively, and defined as follows:
⃒ ⃒
⃒τsim − τexp ⃒
ARE = ⃒⃒ ⃒ × 100%
⃒ (3)
τexp
where τsim and τexp are the simulated and measured IDTs, respectively.
The boxplots are utilized to report and compare the ARE data distribu­
tions of the four models, as displayed in Fig. 3(f). The average and the
median ARE values (marked by the rectangular symbol and the central
line in the box, respectively) of NUIG 1.0 and AramcoMech 3.0 are much
larger than those of Oxymech 2.0 and the modified model. Moreover,
the distribution of the ARE data for Oxymech 2.0 and the modified
model is more concentrated owing to the smaller box length. The eval­
uation of the models using the literature IDT data of different CH4/C3H8
mixtures diluted in N2 is shown in the Supplementary Material and the
modified model also shows good performance.
Fig. 4(a) displays the experimental LFS data from Nilsson et al. [15]
and the simulated results for 80 %CH4/20 %C3H8 mixtures at 1 atm and
298 K and Fig. 4(b) displays the boxplots of the ARE data distributions of
the four models. More simulated results for CH4/C3H8 mixtures diluted
in N2 are shown in the Supplementary Material. It is observed that the
performance of the modified model on LFS predictions is much better
than the Oxymech 2.0 model. Moreover, the LFS simulations using
Modified Oxymech 2.0 for CH4 diluted in CO2 are also shown in the
Supplementary Material, in which the model performs good agreement
with the experimental LFS data. Based on the results of IDTs and LFSs,
the modified model is utilized for the subsequent kinetic analysis.
Source
4.2. Effects of C3H8 addition and O2/CO2 atmosphere

R43 CH4 + H ⇔ CH3 + H2 6.14E + 2.5 9587 [28]

The addition of propane can promote the ignition process, thus
05
R94 CH3 + OH ⇔ CH2OH + H 5.60E + 0.73966 3971 [29] causing shorter IDTs, as shown in Fig. 5. The IDTs decrease significantly
10 with the proportion of C3H8 changing from 0 to 10% but decrease
(Pressure-dependent) slightly with the C3H8 proportion from 10 to 30% in O2/CO2 atmo­
R207 C2H4 + H (+M) ⇔ C2H5 9.57E + 1.463 1355 [30]
spheres, similar to literature results in O2/N2 atmospheres. To investi­
(+M) 08
Low pressure limit 1.42E + − 6.642 5769
gate the effects of C3H8 addition quantitatively, the IDTs of CH4/C3H8
39 mixtures in different ratios need to be obtained in the same condition.
a = -0.569, T3 = 299, T1 = -9147, T2 = 152.4 However, it is difficult to measure the IDTs at the same pressure and
R300 C2H3 + H ⇔ C2H2 + H2 1.70E + 0 0 [31] temperature in a shock tube owing to the variant shock wave attenua­
14
tion. Therefore, the IDTs of CH4/C3H8 mixtures in different ratios were
a
Rate constants are expressed as k = AT b exp(− Ea /Ru T) with units of calories, calculated using Modified Oxymech 2.0 at the same pressure (10 atm)
mole, cm3 and s. and temperature (1400 K) to investigate the effects of C3H8 addition in
both O2/N2 and O2/CO2 atmospheres, as depicted in Fig. 6. It is noted

3
W. Xia et al. Fuel 343 (2023) 127991

Fig. 3. Comparison between experimental and simulated IDTs of CH4/C3H8 diluted in CO2 in this study.

Fig. 4. Performance of four models on LFS predictions of CH4/C3H8 mixtures.

4
W. Xia et al. Fuel 343 (2023) 127991

Fig. 5. Experimental and simulated IDTs of CH4/C3H8 mixtures with different propane additions.

10 atm, T = 1400 K, and Φ = 0.5 in O2/CO2 atmospheres. The brute

force sensitivity in O2/N2 atmospheres is provided in the Supplementary
Material. For the cases in O2/CO2 atmospheres, the decomposition re­
action of propane, C3H8 (+M) ⇔ C2H5 + CH3 (+M) (R327), ranks the 3rd
among the ignition-promoting reactions with the addition of propane
but is absent in the pure methane conditions, as depicted in Fig. 7. Fig. 8
displays the mole fractions of methyl radicals 10 μs after the beginning
for different C3H8 proportions at 1400 K and 10 atm. It is noted that the
concentrations of methyl radicals are negligible in the pure methane
condition but increase significantly with the propane mole fraction
increasing to 30%. With more propane addition, the concentrations of
methyl radicals increase not so significantly, as shown in Fig. 8, which is

Fig. 6. Effects of C3H8 addition on the IDTs of fuel-lean CH4/C3H8 mixtures.

that the addition of 10% propane in the mixtures can significantly

reduce the IDTs. When the proportion of propane exceeds a certain limit
(about 30%), the IDTs of the CH4/C3H8 mixtures are nearly equal to
those of pure propane, i.e. the effects of C3H8 addition are slight, as
expected. The promoting effects of C3H8 addition in O2/CO2 atmo­
spheres are comparable with those in O2/N2 atmospheres. In another
word, the influence of CO2 on the promoting effects of C3H8 addition is
slight.
To further investigate the effects of C3H8 addition, the brute force
sensitivity [36] analysis was introduced. Fig. 7 shows the brute force
sensitivity with different propane proportions in the conditions of P = Fig. 8. Simulated mole fraction of CH3 at different C3H8 proportions.

Fig. 7. Top 10 reactions influencing the ignition in O2/CO2 atmospheres at C3H8 proportion of: (a) 0%; (b) 10%.

5
W. Xia et al.
in line with the case of Fig. 6. According to the rate of production, in the
case with C3H8 addition, the fast increase in the methyl radicals in the
initial stage is through R327 owing to the easier breaking of C-C bonds in
propane, which enhances CH3 + HO2 ⇔ OH + CH3O (R2646), conse­
quently promoting the ignition. Therefore, the addition of propane in
the CH4/C3H8 mixtures can significantly reduce the IDTs of CH4/C3H8
mainly through R327.
As depicted in Fig. 6, the IDTs in O2/CO2 atmospheres are longer
than those in O2/N2 atmospheres. The influence of CO2 on the ignition
consists of physical effects and chemical effects. The former is related to
a high heat capacity of CO2 with respect to N2, which implies a low
adiabatic temperature, whereas the latter is mainly related to CO2 to
directly participate in reactions (effects of reactions with CO2) or indi­
rectly participate in third-body reactions with higher third-body effi­
ciencies than N2 (chaperon effects) [37]. To isolate these effects of the
properties of CO2, two artificial species, A and B, were added to the
kinetic model. The thermochemical properties of species A are the same
as those of CO2, and the chemical properties are inert. Species B has the
same thermochemical properties of CO2 and participates in the third-
body reactions, but does not takes part in the other reaction. There­
fore, the difference in the IDTs between O2/A atmospheres and O2/N2
atmospheres demonstrates the effects of the physical properties of CO2.
Similarly, the difference between O2/B atmospheres and O2/A atmo­
spheres represents the chaperon effects of CO2, while the difference
between O2/CO2 atmospheres and O2/B atmospheres represents the
effects of the reactions with CO2. Fig. 9 displays the percentages of the
effects of the physical and chemical properties of CO2 in the overall
effects on the ignition at 1400 K and 10 atm. The positive value repre­
sents inhibiting effects. For the 90 %CH4/10 %C3H8 mixtures, the
physical effects of CO2 due to the higher volume-specific heat of CO2
compared to N2 are slightly larger than the sum of the chaperon effects
and the effects of the reactions with CO2, and the chaperon effects are
very close to the effects of the reactions with CO2. Moreover, it is noted
that the chaperon effects are comparable to the physical effects for the
pure methane case. According to Liu et al. [21], the inhibiting influence
of the chaperon effects mainly results from 2CH3 (+M) ⇔ C2H6 (+M)
(R2653) for the pure methane case. With the propane addition, the
promoting effects of C3H8 (+M) ⇔ C2H5 + CH3 (+M) (R327) result in the
significant decrease in the inhibiting influence of the chaperon effects.
Therefore, for the CH4/C3H8 mixtures, the ratio of the chaperon effects
on the ignition is the lowest in the total effects of CO2. Compared to the
case of O2/N2 atmospheres, R327, which promotes the ignition, and
R2653, which inhibits the ignition, are both enhanced in the case of O2/
CO2 atmospheres, thus the positive and negative effects due to chaperon
effects of CO2 approximately cancel each other out. Therefore, the ef­
fects of CO2 on the promoting effects of C3H8 addition are slight.
Fig. 9. Physical and chemical effects of CO2 on the ignition at 1400 K and
10 atm.
6
Fuel 343 (2023) 127991
4.3. Effects of equivalence ratio
Fig. 10 displays the measured IDTs of 70 %CH4/30 %C3H8 mixtures
and simulated results by Modified Oxymech 2.0 at the pressure of 1.75
atm and 10 atm with the equivalence ratios increasing from 0.5 to 2.0.
The simulated results by NUIG 1.0 are shown in Fig. S12 in the Sup­
plementary Material. As shown in Fig. 10 (a), the IDTs increase with the
equivalence ratio at 1.75 atm and both the two models can predict the
dependence of IDT on the equivalence ratio. The brute force sensitivity
was calculated using the modified model for different equivalence ratios
at the pressures of 1.75 atm to investigate the effects of the equivalence
ratio. Fig. 11 displays the top 15 reactions with high sensitivity co­
efficients at 1.75 atm and1400 K. As shown in Fig. 11, CH4 + H ⇔ CH3 +
H2 (R2676) makes the largest inhibiting influence on the ignition. With
the equivalence ratios increasing from 0.5 to 2.0, the order of C3H8 + H
⇔ n-C3H7 + H2 (R348) rises from the 11th to 4th, while reaction C3H8 +
H ⇔ i-C3H7 + H2 (R332), also inhibiting the ignition, rises from the 16th
to 9th (not shown in Fig. 11). It is also noted that the order of reaction
2CH3 (+M) ⇔ C2H6 (+M) (R2653) rises from 5th to 2nd due to the
increasing CH3 radicals with the equivalence ratios from 0.5 to 2.0.
These indicate that the inhibition effects of the hydrogen-abstraction
reactions of fuels by H radicals and the recombination of CH3 radicals
were strengthened in fuel-rich conditions due to the higher fuel con­
centration. The net reaction rates of the reactions above increase with
the equivalence ratio. Therefore, the IDTs of CH4/C3H8 mixtures diluted
in CO2 increase with the equivalence ratio at the pressure of 1.75 atm.
As shown in Fig. 10 (b), no statistical difference is observed between
the measured data of different equivalence ratios at 10 atm, which is
similar to the IDTs of C3H8 diluted in CO2 [23]. Modified Oxymech 2.0
and NUIG 1.0 can both reproduce the independence of IDT on the
equivalence ratio at 10 atm. Fig. 12 shows the brute force sensitivity for
three equivalence ratios at 10 atm and 1300 K. As depicted in Fig. 12, H
+ O2 (+M) ⇔ HO2 (+M) (R2563), a pressure-dependent reaction, is
significantly enhanced at 10 atm. R2563 ranks 10th among the ignition-
suppressing reactions in fuel-lean conditions, inhibiting the ignition,
while it ranks 6th among the ignition-promoting reactions in stoichio­
metric conditions, promoting the ignition due to the enhancement of
CH3 + HO2 ⇔ OH + CH3O (R2646). Because the increase in the con­
centration of O2 with the decreasing equivalence ratio from stoichio­
metric to fuel-lean conditions promotes the ignition due to the
hydrogen-abstraction reactions of fuels and the recombination of CH3
radicals, which is comparable to the inhibition effect of R2563, the IDTs
of the CH4/C3H8 mixtures in fuel-lean conditions are very close to those
in stoichiometric conditions. From Fig. 12, R2563 ranks 4th among the
ignition-promoting reactions in fuel-rich conditions, promoting the
ignition. Because the increase in the mole fraction of fuels with the
increasing equivalence ratio from stoichiometric to fuel-rich conditions
inhibits the ignition, which is comparable to the positive effect of R2563,
the IDTs of the CH4/C3H8 mixtures in fuel-rich conditions are very close
to those in stoichiometric conditions. Therefore, there is no statistical
difference observed between these measured data of different equiva­
lence ratios at 10 atm.
5. Conclusion
The auto-ignition properties of methane/propane mixtures in ratios
from 90/10% to 70/30% diluted in CO2 were measured at equivalence
ratios of 0.5, 1.0, and 2.0; pressures of 1.75 and 10 atm; and tempera­
tures in the range of 1240–1520 K in a shock tube. Four key reactions in
the Oxymech 2.0 model were updated and the modified model shows
reasonable performance in both the IDT and the LFS predictions in O2/
N2 and O2/CO2 atmospheres.
The addition of propane promotes the ignition significantly in the
C3H8 proportion range from 0 to 30% in both cases of CO2 and N2 but
has slight effects on the ignition with the C3H8 proportion more than
30%. The fast increase in the methyl radicals in the initial stage is
W. Xia et al. Fuel 343 (2023) 127991

Fig. 10. Experimental and calculated IDTs of CH4/C3H8 mixtures at different equivalence ratios.

Fig. 11. Top 15 reactions influencing the ignition in different equivalence ratios at 1400 K and 1.75 atm.

through C3H8(+M) ⇔ C2H5 + CH3 (+M) owing to the easier breaking of
C-C bonds in propane, which enhances CH3 + HO2 ⇔ OH + CH3O,
consequently promoting the ignition. The physical effects of CO2 due to
the higher volume-specific heat of CO2 compared to N2 are slighter
larger than the chemical effects of CO2, and the chaperon effects are very
close to the effects of the reactions with CO2. The effects of CO2 on the
promoting influence of the propane addition are slight. The chaperon
effects of CO2 sourced from R327 and R2653 impact the promoting
effects of the propane addition. The positive (from R327) and negative
effects (from R2653) due to chaperon effects of CO2 approximately
cancel each other out.
The IDTs increase with the equivalence ratio at the pressure of 1.75
atm but there is no statistical difference observed between these
measured data of different equivalence ratios at 10 atm. The negative
effects of H-abstraction reactions by H radicals of the fuel molecules
increase with the equivalence ratio at 1.75 atm. H + O2(+M) ⇔

7
W. Xia et al.
Fig. 12. Top 18 reactions influencing the ignition in different equivalence ratios at 1300 K and 10 atm.
HO2(+M) suppresses the ignition at the fuel-lean condition but promotes
the ignition in stoichiometric and fuel-rich conditions at 10 atm.
CRediT authorship contribution statement
Wenxiang Xia: Investigation, Formal analysis, Writing – original
draft. Chun Zou: Methodology, Supervision, Writing – review & editing.
Yi Yuan: Investigation, Data curation, Validation. Rui Fu: Data cura­
tion. Jiacheng Liu: Data curation. Chao Peng: Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
This work was supported by the general program (52276111) of the
National Natural Science Foundation of China.
8
Fuel 343 (2023) 127991
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2023.127991.
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