Fuel 302 (2021) 121137

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

Full Length Article

Development of the chemical kinetic mechanism and modeling study on the

ignition delay of liquefied natural gas (LNG) at intermediate to high
temperatures and high pressures
Solmaz Nadiri a, b, *, Sumit Agarwal a, Xiaoyu He a, b, Ulf Kühne b, Ravi Fernandes a, b, Bo Shu a
a
Department of Physical Chemistry, Physikalisch-Technische Bundesanstalt, Braunschweig, Germany
b
Institute of Internal Combustion Engines, Technische Universität Braunschweig, Braunschweig, Germany

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

Keywords: In the past decade, liquefied natural gas (LNG) has attracted attention as a sustainable energy resource. The
LNG composition of LNG is one of the primary factors that has an influence on the engine knock and determines the
Modeling fuel reactivity and the heat release in the combustion processes due to the presence of C1-C5 alkanes. The
Reaction kinetics
knocking behavior of LNG in gas engines is derived by the methane number (MN) which is directly related to the
Ignition delay
composition of the mixtures and the operating conditions. The determination of the methane number therefore
Rapid compression machine
Shock tube demands a comprehensive characterization of a fuel mixture towards its auto-ignition properties such as ignition
delay time (IDT) based on chemical kinetics of the fuel oxidation.
In this study, a detailed chemical kinetic mechanism was developed to discover a correlation between the MNs
and IDTs. The comparison of the modeling and experiments results of the ignition of different LNG mixtures
containing C1-C5 alkanes and N2, and reference mixtures containing only CH4 and H2 with known MN were
carried out in the temperature range 850–1550 K, at pressures of 10, 20 and 40 bar, and equivalence ratios (ϕ) of
0.4 and 1.2. The newly developed model demonstrates very good performance in simulating the IDT of various
LNG mixtures, while the improvement in reduction of the maximal discrepancies between model and experi­
ments is from factor 7–10 to 1–2. Moreover, the modeling studies provided a deeper understanding of the
oxidation chemistry of the investigated mixtures.

1. Introduction
In last decades, natural gas has attracted strong interest of energy
and mobility sectors as energy carrier [1] due to its dominant advan­
tages including low greenhouse gas emissions [2,3] and high conversion
efficiency in energy production [4]. Liquefied natural gas (LNG) is the
liquid form of natural gas generated by condensing the natural gas at
atmospheric pressure to − 162 ◦ C [5].
The composition of LNG depends upon the sources from which the
natural gas is extracted, and in general, LNG is constituted particularly
of methane (79–99%) and a small portion of ethane, propane, butane, or
pentane and most often<1% nitrogen [6].
In general, the fuel composition is one of the fundamental factors
that have an influence on the engine knock and ascertains the fuel
reactivity and the heat release in the combustion processes [7,8]. The
propensity of fuels to cause engine knock at typical operating conditions
are associated with their ignition properties, in particular the ignition
delay time (IDT).
The engines powered by LNG were designed based on the gasoline
engines or diesel engines [9], whereas lack of high torque at a slow speed
and loss of optimal functioning during the acceleration process [10]
have attracted interest from researchers [11–15] to improve the per­
formance of LNG engines by increasing the engine compression ratio or
enhancing gas engines performance by adding a turbocharge [16].
These approaches increase the cylinder pressure and temperature,
which increases the knocking tendency [17].
Engine knock always leads to harmful consequences for internal
combustion engines. The knock inhibiting methods, such as water in­
jection [18], relies on highly accurate knock prediction. However, the
sophistication and diversity of the natural gas composition from source
to source usually constitute an obstacle to predict and control the engine
knock. Hence, it is necessary to characterize the knock resistance of

* Corresponding author.
E-mail address: solmaz.nadiri@ptb.de (S. Nadiri).

https://doi.org/10.1016/j.fuel.2021.121137
Received 14 January 2021; Received in revised form 9 April 2021; Accepted 25 May 2021
Available online 4 June 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
S. Nadiri et al.
natural gas with different compositions. For gasoline, the octane number
(ON) has been estimated to evaluate the anti-knock performance of this
liquid fuel [7]. Gasoline is compared to the iso-octane/n-heptane mix­
tures with the same anti-knock capacity in a test engine. But ON has
shown limitation for characterizing the gaseous natural gas, which
normally has higher knock resistance than gasoline (ON > 100). As a
counterpart of ON, the concept of methane number (MN) was proposed,
which applies hydrogen/methane mixtures as references [8].
The knocking properties of LNG are characterized by MN demon­
strating the competence of fluid to resist knocking in engines [19]. A
higher MN value points out a gas fuel with higher quality preventing
knocking and engine power reduction consequently. The MN is the LNG
equivalent of octane number for gasoline. The MN of pure methane is
100 which has high knocking resistance during fuel combustion. On the
contrary, the MN of pure hydrogen is defined as 0, which gives high
knocking tendency during engine operations [20]. To determine a
comprehensive method to establish a relationship between gas compo­
sition and MN, several standards have been proposed. The earliest MN
measurements of LNG can be traced back to the Anstalt für Ver­
brennungsmotoren Prof. Hans List (AVL) method proposed in 1971 [21]
which covers hydrocarbons only up to butane (C4). Subsequently, the
AVL method has been formulated once more by Motoren-Werke Man­
nheim (MWM) taking the heavier hydrocarbons more precisely into
account and considering the nitrogen’s impact on MN in a different way
[22]. Besides, a novel algorithm, namely, the National Physical Labo­
ratory (NPL) algorithm, was developed by Gieseking and Brown [22]
applying the huge dataset from AVL and considering the hydrocarbons
up to C4 and the hydrocarbon higher than C4 are treated as butane for
the MN calculation. Most recently, the NPL algorithm was improved
taking into account the influence of iso- and normal-compositions of
butane and pentane on the MN of an LNG mixture at Technical Uni­
versity of Braunschweig (TUBS) [23]. Therefore, new weighting factors
were adjusted in the NPL algorithm for iso- and normal butane and
pentane. These factors have been validated against 23 different LNG
mixtures [24].
To date, extensive research on the ignition of fuels containing only a
single component of alkane groups have been carried out [25–29], but
few studies have investigated the ignition of multi-components fuels.
Vallabhuni et al. [30] conducted a series of experiments in a high-
pressure shock tube (ST) and a rapid compression machine (RCM) to
study the oxidation of LNG mixtures containing CH4/C2H6/C3H8/n-
C4H10/i-C4H10/n-C5H12/i-C5H12/N2 with different compositions over
the temperature range of 850–1450 K, pressures of 20 and 40 bar, and at
equivalence ratios of 0.4 and 1.2. The experimental results were simu­
lated using two kinetic mechanisms, whereas good agreement was
observed between the kinetic model and the measurements at high
temperatures but noticeable disagreement at intermediate temperatures
for some LNG mixtures that contains high fraction of ethane [30].
A recent study by Shu et al. [31] involved the investigation of the
ignition property of 11 different LNG mixtures containing CH4/C2H6/
C3H8/n-C4H10/i-C4H10/n-C5H12/i-C5H12/N2 with MN from 70 to 80 and
five reference mixtures containing only CH4 and H2 with MN from 50 to
90, in a high-pressure shock tube (HPST) and a rapid compression ma­
chine at pressures of 10, 20, and 40 bar, temperatures between 870 and
1525 K, and two equivalence ratios of 0.4 and 1.2, while the MN
determined applying the MWM algorithm. It has conclusively been
demonstrated that for the LNG mixtures, the mixture with MN 70 clearly
showed higher reactivity than the mixture with MN 80. Besides, for the
reference mixtures, the IDTs of the mixture with MN 90 were longer than
the mixture with MN 50. In an analysis of different mixtures with the
MN of 80, it was shown that the reactivity of the mixture containing
more ethane is higher, resulting in a higher knocking propensity in en­
gine operations. Apart from few experimental investigations of LNG
mixtures, numerical studies have been extensively performed to
construct comprehensive chemical kinetic mechanism for alkanes up to
C5.
2
Fuel 302 (2021) 121137
Mehl et al. [32,33] developed a mechanism based on a comprehen­
sive mechanism of Curran et al. [34] for oxidation of iso-octane. The iso-
octane and n-heptane mixture oxidation were carried out in a shock tube
and a rapid compression machine with the pressure from 3 to 50 atm,
the temperature from 650 to 1200 K, and equivalence ratios from 0.3 to
1.0. The mechanism showed a good agreement at low and high tem­
perature, over the whole pressure range for very lean and stoichiometric
conditions. Afterwards, Zhang et al. [35] studied the oxidation of n-
heptane in air over the temperature range of 726–1412 K, at pressures of
15, 20 and 30 bar and at equivalence ratios of 0.25 and 4.0 in two
different high-pressure shock tubes. A detailed kinetic mechanism con­
taining the sub-mechanisms of n- pentane, n- hexane and n -heptane has
been developed by implementing the experimental data and other
modeling work to depict the oxidation of n-heptane and has been vali­
dated with experimental data from their work and the literature. They
showed that the model predicts the experimental data with a good
agreement.
In both recent studies by Vallabhuni et al. [30] and Shu et al. [31],
the NUIG n-hexane mechanism [36] and LLNL’s n-heptane mechanism
[37] have been validated, while good agreement between simulation
and experiments has been restricted to high temperature ignition con­
ditions and significant discrepancies were observed at intermediate to
low temperatures. However, low temperature combustion (LTC) is
particularly important due to its promising low amount of particulate
matter (PM) and nitrogen oxides (NOx) emissions potential. A notable
example of low temperature combustion application is the advanced
engine concept homogenous charge compression ignition (HCCI) which
utilizes a compressed premixed fuel–air mixture to accomplish clean
combustion [38]. HCCI is considered as a promising engine combustion
process because it can improve the thermal efficiency of spark ignition
engine and lower the NOx and PM formation of compression ignition
engine. However, one of the main obstructions to realize HCCI is the
difficulty in combustion phasing control, which mainly relies on the
knowledge of the auto-ignition chemistry of the fuel–air mixture [39].
Therefore, a reliable mechanism for LNG auto-ignition is helpful for
predicting the HCCI working condition of LNG-fueled engine. Due to the
limited performance of the mechanisms in the literature, it is crucial to
further develop the chemical kinetic mechanism for LNG under LTC
conditions.
The specific objective of this study was to develop a natural gas ki­
netic mechanism appropriate for low temperature ignition conditions
and especially for lean fuel–air mixtures which represent typical HCCI
engine operating conditions. Experimental data applied for this study
were partly collected using Shu and co-workers’ measurements of 11
different LNG mixtures with MWM-MN of 73–80 (TUBS-MN of
67.8–81.1) and 5 different reference mixtures and 5 additional LNG
mixtures investigated in this work. The detailed compositions of the LNG
mixtures and the reference mixtures of [31] and this work categorized in
terms of MNs are provided in Table 1.
In this study, the new TUBS algorithm [23], which is based on the
NPL algorithm; was employed to determine the MN of the mixtures. The
gas composition was defined to investigate the effect of C4 and C5 iso­
mers on the IDTs. To compare the chemistry of different molecular
structures, 5 more LNG mixtures were added, namely mixture 4 (TUBS-
MN 74.1), mixture 5 (TUBS-MN 74), mixture 6 (TUBS-MN 72.9),
mixture 11 (TUBS-MN 77.3) and mixture 13 (TUBS-MN 77.1). The
corresponding measurements were carried out for equivalence ratios (ϕ)
of 0.4 and 1.2 in HPST according to the temperatures and pressures of
Shu and co-workers’ measurements for each group with similar MN.
In addition, due to the lack of detail for low temperature combustion
of mixtures containing 1.0% C4H10 and 0.2% C5H12 and the reference
mixtures, the investigation of combustion of mixture 7 (TUBS-MN 73.3)
and mixture 12 (TUBS-MN 76.4) were performed, respectively, in RCM
at equivalence ratio of 0.4, pressures of 20 and 40 bar, and temperatures
870–990 K. Subsequently, the investigation of combustion of reference
mixtures of 50, 70 and 90 were performed in RCM at equivalence ratio of
S. Nadiri et al. Fuel 302 (2021) 121137

Table 1
Compositions (% volume) of the tested LNG Mixtures and reference mixtures in the HPST and the RCM.
Mixture CH4 C2H6 C3H8 n-C4H10 i-C4H10 n-C5H12 i-C5H12 N2 H2 TUBS-MN MWM-MN Ref.

Mix 1 91.83 5.83 1.833 0.5 79.1 80 [31]

Mix 2 89.4 10.1 0.5 81.1 80
Mix 3 94.5 5.0 0.5 79.8 80

Mix 4 96.6 1.45 1.45 0.5 74.1 80 This work

Mix 5 90.915 5.78 1.81 1 0.5 74 73 This work
Mix 6 90.915 5.78 1.81 1 0.5 72.9 73
Mix 7 90.915 5.78 1.81 0.5 0.5 0.5 73.3 73 [31]

Mix 8 89.99 5.71 1.80 2 0.5 69.8 70 [31]

Mix 9 89.99 5.71 1.80 2 0.5 67.8 70
Mix 10 89.99 5.71 1.80 1 1 0.5 68.7 70

Mix 11 91.66 5.82 1.83 0.2 0.5 77.3 76 This work

Mix 12 91.66 5.82 1.83 0.2 0.5 76.4 76 [31]
Mix 13 91.66 5.82 1.83 0.1 0.1 0.5 77.1 76 This work

Mix 14 91.46 5.81 1.83 0.4 0.5 75.2 74 [31]

Mix 15 91.46 5.81 1.83 0.4 0.5 73.8 74
Mix 16 91.46 5.81 1.83 0.2 0.2 0.5 74.7 74

Ref 50 50 50 50 50 [31]
Ref 60 60 40 60 60
Ref 70 70 30 70 70
Ref 80 80 20 80 80
Ref 90 90 10 90 90

0.4, pressures of 20 bar, and temperatures 950–1040 K. The detailed
experimental conditions of this work and [31] are presented in the
Supplementary Material (Table S1). The entire results of this work will
bring an updated mechanism for the LNG ignition and provide the
correlation between the MNs and the IDTs, which has not been done in
the past and it will provide valuable insight to the application of LNG as
a transport fuel.
2. Methods
2.1. Experimental setup
2.1.1. Shock tube facility
The shock tube experiments involving IDTs on the LNG were carried
out on a high-pressure shock tube (HPST) at the Physikalisch-Technische
Bundesanstalt (PTB), Germany. The HPST can provide post-shock con­
ditions up to 200 bar and 3000 K respectively. Comprehensive details of
this HPST have been reported in our previous work [31], so only a brief
description will be given here. The stainless-steel HPST has an overall
inner diameter of 70 mm and a total length of 8 m (Fig. 1).
Both driver and driven section can be pumped down to a vacuum
pressure of 5E-05 mbar using a turbomolecular pump. The HPST can
sustain post shock conditions up to 3000 K and 1000 bar. The LNG fuel
mixtures were prepared in a 50 L mixing vessel equipped with a
magnetically driven stirrer, which requires a time duration of 1 h for the
mixtures to be completely homogenized. The mixtures were produced
from PRAXAIR with uncertainty in each component of about < 2%.
Further, the reference mixtures were made in the lab applying high-
purity CH4 and H2 (>99.999%, Linde).
The incident shock velocity at the end wall is determined by linear
extrapolation of the velocity profile between the four piezoelectric
pressure transducers (Kistler 603C) installed at equal distance along the
last 2 m of the driven section. The 1-dimensional shock-jump equations
were used to calculate the pressure and temperature (P5 and T5) behind
the reflected shock wave. Further, the end-wall of the driven section also
houses another pressure sensor placed at the center of the flange to
measure the pressure behind the reflected shock in turn allowing one to
measure the IDTs. Fig. 2 demonstrates a typical pressure profile and the
corresponding derivative of the pressure with respect to time (dp/dt)
from a shock tube experiment, whereas onset of ignition is the local
maximin of dp/dt. The IDT is defined as the time between the arrival of
the reflected shock wave and the steepest rise in pressure due to ignition.
Fig. 3 illustrates the IDTs of the LNG mixtures, namely, Mixture 4, 5,
6, 11 and 13, measured in this work in HPST at 10 and 20 bar and
equivalence ratios of 0.4 and 1.2 in the temperature range 1160–1480 K.
It can be seen that the IDTs at 10 bar are very close to each other and

Fig. 1. Schematic of the high-pressure shock tube (HPST) facility at PTB, Germany [40].

3
S. Nadiri et al. Fuel 302 (2021) 121137

Fig. 4. Schematic of a single-piston Rapid Compression Machine (RCM) facility

Fig. 2. Typical pressure profile from a shock tube experiment for LNG fuels. at PTB, Germany.

The pressure profiles were measured using a Kistler 601H pressure

transducer connected with a 5018-type charged amplifier and recorded
via a Spectrum data acquisition card (M2i.3016-Exp) that can further be
applied to determine the IDTs. A photomultiplier has also been applied
to monitor the OH* chemiluminescence near 307 nm to track the igni­
tion onset. The same test mixtures that are utilized in the shock tube are
manometrically prepared in a 10-L stainless steel tank. Argon and Ni­
trogen (>99.999% pure, Linde) was utilized as the bath gas to obtain the
desired compression temperature. Fig. 5 represents a typical pressure
trace from an LNG mixture. The mixture as seen in the figure is com­
pressed to a first pressure peak (which is the EOC), followed by a slow
pressure drop caused by the loss of heat encountered at the reactor walls
until the second steep rise in pressure indicating the onset of ignition.
The ignition point is defined as the point where the first derivative of
pressure reaches the peak and IDT, in RCM is defined as the interval
between the EOC and the ignition point as shown in Fig. 5.
Fig. 3. IDTs of LNG mixtures measured in this work in HPST at 10 and 20 bar,
All gas mixtures were prepared at least 3 h before ensuring complete
ϕ = 0.4 and 1.2.
homogeneity of the mixture. Moreover, a non-reactive mixture was also
prepared in one of the cylinders by substituting the oxygen by nitrogen
equivalence ratio does not show large impact on the IDT. IDTs at 20 bar
to characterize the heat loss of each measurement. The reactive com­
are clearly shorter than that at 10 bar, however, the differences between
bustion temperature from the combustion chamber is not obtained
different mixtures are negligible due to their very closed methane
numbers.

2.1.2. Rapid compression Machine facility

The ignition measurements at low to intermediate temperatures have
been performed in a Rapid Compression Machine (RCM). The RCM has
been elaborated in detail in the Ref. [41], so here it will be described
briefly. The RCM facility consists of a pneumatically driven and hy­
draulically braked single-piston drive. It has a 50-mm-inner-diameter
combustion chamber, which houses 6 ports with an inlet–outlet port,
pressure transducer, OH* Chemiluminescence, and a dynamic temper­
ature sensor respectively. Fig. 4 demonstrates the schematic of this RCM.
The facility can sustain a maximum pressure of 200 bar and a working
temperature range of 600–1150 K at the end of compression (EOC). The
variation of temperature at EOC (TC) was realized by changing the initial
temperature via heating tapes installed on the outer surface of the
combustion chamber, cylinders, and the complete manifold. The
compression ratio of the combustion chamber is kept at 20.93 to rule out
changes in the heat loss characteristics of the RCM. The compression
ratio was determined by the ratio between the geometrical volume of the
combustion chamber at the bottom dead center (BDC) and that at the top
dead center (TDC). Both included the dead volume of the gas inlet. The Fig. 5. Representation of the typical ignition delay data from a Rapid
stroke length and the diameter of the chamber were measured by a Compression Machine facility showcasing Reactive (blue line), non-reactive
(red line), and the OH* Chemiluminescence signals. (For interpretation of the
vernier scale and the dead volume of the gas inlet were calculated ac­
references to color in this figure legend, the reader is referred to the web
cording to the technical drawing.
version of this article.)

4
S. Nadiri et al.
directly, but rather it is a derived quantity. TC at the end of the
compression is related indirectly to the measured pressure and the
specific heats based on the adiabatic core hypothesis [42]. It is assumed
that the heat loss only happens between the boundary layer of the
combustion chamber to the wall and the gas in the core undergoes
adiabatic compression and expansion. Applying the creviced piston can
avoid the roll-up vortex arising from the piston movement, so that the
core gas is not disturbed by the boundary layer [43]. Since then, Tc can
be calculated through the following equation according to adiabatic
process of ideal gas:
∫TC
PC γ(T) dT
ln = (1)
P0 γ(T) − 1 T
T0
where, P0 and T0 are the initial pressure and temperature in the reaction
chamber, respectively, and γ is the specific heat of the initial mixture.
Fig. 6 illustrates the IDTs of the LNG mixtures, namely, mixture 7 and
12, and reference mixtures of 50, 70 and 90, measured in this work in
RCM at 20 and 40 bar and equivalence ratio of 0.4 in the temperature
range 875–1040 K. Unlike the data measure in HPST, the IDTs measured
in RCM show clear differences among the mixtures, and the IDTs become
shorter as the methane number is smaller, i.e., Ref 50–90, and Mix 7
(TUBS-MN 73.3) to Mix 12 (TUBS-MN 76.4). However, the IDTs of
reference mixtures cannot be correlated to the real LNG mixtures, this
will be discussed more in a later section.
2.1.3. Uncertainty
The uncertainty in the HPST comprises of uncertainty of the gas
composition, the primary state of the gas mixture, and the incident
shock velocity. The uncertainty in gas composition involves the uncer­
tainty in the equivalence ratio, mean molecular weight, and the uncer­
tainty in the specific heat ratio. Moreover, as explained in Section 2.1.1,
the mixtures were prepared from PRAXAIR with an uncertainty of below
2% for each component. Upon calculating the partial pressure of each
component gas in the LNG mixture and the reference gas, the error in
equivalence ratio comes out to be 0.005 for both cases. Using the mo­
lecular weight of each component gas, the error in mean molecular
weight is estimated as 0.031 kg/kmol. Further, the specific heat ratio’s
uncertainty is estimated as 0.002, considering the error of argon content
in the mixtures. The incident shock velocity was inferred by extrapo­
lating the signal captured from the four different sensors fitted at the last
2 m section of the driven tube, thereby utilizing the least square method
to obtain the final value. The uncertainty of shock velocity depends on
the uncertainty of the sensor, sensor position, of the measured points
(<1 m/s), and the standard error involved with the least square method
(<5 m/s). The overall uncertainty in the shock velocity measurement
comes out to be approximately 8 m/s. The uncertainty involved with the
Fig. 6. IDTs of LNG mixtures and reference mixtures measured in this work in
RCM at 20 and 40 bar, and ϕ = 0.4.
5
Fuel 302 (2021) 121137
primary state of the gas mixtures includes the initial pressure and tem­
perature. The uncertainty involved in the initial temperature is a stan­
dard 2.2 K, and for the initial pressure is a standard 0.1 mbar (0.25%)
considering the Baratron pressure measurement apparatus. Finally,
summing up all the involved uncertainties, the overall shock tube
measurement uncertainties comes out to be approximately 5%.
Likewise, the uncertainty of the experimental data in the RCM in­
volves the repeatability of the experiments and the measurement un­
certainty. To assure the statistical significance, the repetition of
measurement for reactive mixtures has been performed for at least three
times. A recent study of our group by He et al. [41] reported that the
overall uncertainty of the IDTs implies consequence from 5% uncer­
tainty in repeatability and from about ± 10 K uncertainty in the com­
pressed temperature. They investigated in the supplementary materials
that the uncertainty of the compressed temperature depends on the
initial temperature and pressure of the gas mixture, compressed pres­
sure, and the heat capacity ratio. In addition, it is indicated in their study
that the effect of the uncertainties of compressed pressure and mixture
composition is already considered in the uncertainty of compressed
temperature, and the IDT significantly changes with temperature than
with any other parameter, thus the direct impact of the uncertainty of
compressed pressure and mixture composition on IDT can be neglected.
In this work, Eq. S1 in the supplementary material given by He and co-
workers [41] was applied to calculate the uncertainty of the compressed
temperature in RCM.
3. Modeling
An in-house codes of Cantera [44] version 2.4.0 was used for all
simulations performed in this study. To represent the mixtures con­
taining multiple species and compute the thermodynamic and kinetic
properties of the mixtures, class Solution was used. In applying class
Solution, two independent thermodynamic properties are essential to
specify the thermodynamic state of the mixtures. Furthermore, to create
a constant volume reactor, an IdealGasReactor and a Reservoir, two
instances of class Reactor, were employed. An IdealGasReactor provides
equations that are exclusively for the ideal gas equation of state and was
selected over the class Reactor in the modeling of the reactor since it can
solve the equation of energy directly from temperature, instead of the
enthalpy [45]. The Reservoir creates the surrounding environment of
the reactor, containing a nonreactive perfectly mixed infinite amount of
fluid -in this work air- with no effects on the composition and thermo­
dynamic state of the mixtures. The IdealGasReactor and the Reservoir
were separated by a class Wall. The results of the simulation by Cantera
were compared to the CHEMKIN-PRO [46] software results that showed
negligible differences.
Given that the raw outputs of the reactors as the pressure profiles
were not smooth and comprised of plenty of noises in small amplitude,
they were filtered and flattened by smooth function without any changes
to the nature of the signals. Fig. 7 represents a typical pressure profile
along with the smoothed pressure profile from an RCM experiment for
the non-reactive mixture, while a portion of the figure is magnified and
inserted as a subfigure to provide a deeper understanding. The red line
depicts a smoothed pressure profile with the exact similar trend to the
original one.
3.0.1. Shock tube simulation
The measurements of IDT in the shock tube were modeled assuming
a 0-D homogeneous adiabatic reactor at a constrained volume. The
voltage signals as the outputs of the dynamic pressure transducer of the
shock tube were extracted and converted to the pressure profile by a
scaling factor set by the operator to derive the volume profile out of the
pressure profile from the beginning of the reflected shock wave until the
ignition onset assuming that the whole process is isentropic. From the
ignition onset until the end of the simulation, the volume was assumed
S. Nadiri et al.
Fig. 7. Schematic of the original pressure profile and the smoothed pres­
sure profile.
constant. This volume profile was used to generate the simulated pres­
sure profile and calculating the IDT subsequently. In general, assuming a
constant volume reactor from beginning to the end of the ignition pro­
cess has an impact on the predictability of the model and leads to
calculating a shorter IDT in comparison to the experimental IDT.
3.0.2. RCM simulation
In RCM, due to the disturbance in consequence of the compression
stroke and heat loss from the core region to the walls of the reaction
chamber, the reactor volume was considered inconstant. As explained
earlier, non-reactive experiments were carried out for each case with the
specified temperature, pressure, and equivalence ratio to generate the
volume profile using the adiabatic core assumption. The procedure of
creating the volume profile was as follows: first, the initial mass-specific
entropy (S0) was recorded by assigning a Cantera Solution object at the
initial pressure (P0) and temperature (T0) of the reactor. Then, the
pressure at each data point (Pi) from the non-reactive pressure profile
and formerly recorded S0 set the state of the Solution object, especially
the temperature at each data point, successively. Therefore, the volume
(Vi) at each data point was calculated based on the ideal gas law:
P0 Ti
Vi = V0 × × (2)
Pi T0
where Ti is the temperature at each point calculated by the Cantera
Solution and V0 is the initial volume that was assumed 1 m3, while this
value was applied in creating the reactor to set the initial volume of the
reactor as well. A typical volume profile generated from the pressure
profile is given in the Fig. S1 in the Supplementary Material.
The generated adiabatic volume profile was used to a reactive
simulation in Cantera by setting the initial state of the reactor at T0 and
P0 and installing an IdealGasReactor and a Reservoir with a Wall sepa­
rating them. Eventually, the resulted pressure profiles were applied to
define the simulated IDTs.
3.0.3. Kinetic model
Two mechanisms, namely, the National University of Ireland Gal­
way’s (NUIG) pentane isomers mechanism [47–49] and Lawrence Liv­
ermore National Laboratory’s (LLNL) iso-octane mechanism [32,33]
which cover all the species existing in the LNG mixtures, were adopted
for the kinetic modeling of the ignition of LNG at high pressures and low
to intermediate temperatures.
The NUIG pentane isomers mechanism consists of 697 species and
3214 reactions. It contains the sub-mechanisms of dimethyl ether, iso­
butene and every three isomers of pentane. Bugler et al. [49] have
6
Fuel 302 (2021) 121137
demonstrated that the NUIG pentane isomers mechanism shows a good
quantitative agreement with the experimental data from the measure­
ment of IDTs of pentane isomers in a shock tube and a rapid compression
machine at equivalence ratios of 0.5, 1.0, and 2.0 at pressures of 1, 10,
and 20 bar and at intermediate to high temperatures.
The LLNL group has published several alkane mechanisms where the
LLNL’s iso-octane mechanism contains the sub mechanisms up to C5.
However, LLNL’s iso-octane mechanism does not include all the pentane
isomers, namely, iC5, LLNL’s n-Heptane [33,37] and iso-octane mech­
anism were merged together to generate a mechanism which covers all
the components contained in the selected LNG mixtures. In this work,
the LNG mixtures are composed of hydrocarbons only from C1 to C5,
therefore the hydrocarbons from C6 to C8 were eliminated from the
merged mechanism. The resulting mechanism consists of 497 species
and 3950 reactions. Both LLNL’s iso-octane and LLNL’s n-Heptane
mechanisms have been validated against several experimental results in
shock tubes and RCM under the pressure of 1–55 atm, temperature of
900–1450 K, and with stoichiometric and lean air–fuel mixtures
[50–53]. Therefore, they were employed in chemical kinetic modeling
to calculate the IDTs.
Moreover, to get a deeper insight into the main elementary reactions
that control the IDTs, sensitivity analyses were carried out. A brute force
algorithm was employed to execute the sensitivity analysis. In this al­
gorithm, first, the rate coefficient (ki) of all of the reactions in the
mechanism was doubled separately in each loop, and then a Solution
object was set to the initial state of the reactor (T0, P0). As the solver
reached the end of the loop, the rate coefficient of the aforementioned
reaction was set to its original value. The sensitivity coefficient of a
particular reaction to the IDT (τ) is described as follow:
τ(2ki) − τ(ki)
Sensitivity coefficient = (3)
τ(ki)
A positive sensitivity coefficient indicates that if the rate coefficient
for a reaction is increased, that reaction hinders the ignition event and
will increase the calculated IDT and vice versa.
4. Results and discussion
4.1. Chemical kinetic mechanism development
The NUIG pentane mechanism and the merged LLNL mechanism
have been first validated against the newly measured IDTs in the HPST
and the RCM. Although the simulation based on the merged LLNL and
NUIG mechanisms showed a good agreement with the experimental data
resulting from the measuring of IDTs of the LNG mixtures in HPST at
high temperatures for both equivalence ratios, significant discrepancies
were observed in the modeling for the RCM results. Two mixtures with
different MN, namely mixture 7 (TUBS-MN 73.3) and mixture 12 (TUBS-
MN 76.4) were selected to represent the results in the simulation of
HPST and RCM. More comparisons can be found in the Fig. S2 in the
Supplementary Material. Fig. 8 depicts the comparison between the
simulated and measured IDTs of both LNG mixtures namely mixture 7
(TUBS-MN 73.3) and mixture 12 (TUBS-MN 76.4) at 10 and 20 bar,
1200–1470 K, and ϕ = 0.4 and 1.2. As can be seen, both NUIG and
merged LLNL mechanism gave almost identical results and simulated
IDTs agree to the experimental data excellent.
Fig. 9 demonstrates the IDTs from simulation and experiments of
mixture 7 and mixture 12 at 20 and 40 bar, 880–1000 K and ϕ = 0.4.
Unlike the good agreement found at high temperatures, both NUIG and
merged LLNL mechanisms calculated longer IDTs compared to the
experimental data at intermediate temperatures, while these discrep­
ancies are larger at 40 bar than those at 20 bar. In addition, the model
was not able to predict the ignition at 880 and 927 K for mixture 7 and at
885 K for mixture 12.
The sensitivity analyses for mixture 7 and 12 at 900 and 1200 K
provided in the Supplementary Material (see Figs. S3 and S4) prove that
S. Nadiri et al. Fuel 302 (2021) 121137

Fig. 8. IDTs of LNG mixtures measured in the HPST [31]. A) Mixture 7 (TUBS-MN 73.3) at 10 bar, ϕ = 0.4 and 1.2, B) Mixture 12 (TUBS-MN 76.4) at 10 and 20 bar,
ϕ = 0.4. (Symbols: experimental points; Lines: model predictions).

Fig. 9. IDTs of LNG mixtures measured in the RCM at 20 and 40 bar, ϕ = 0.4. A) Mixture 7 (TUBS-MN 73.3), B) Mixture 12 (TUBS-MN 76.4) (Symbols: experimental
points; Lines: model predictions).

both mechanisms have a same performance at high temperature, but the

sensitivity coefficients corresponding to the reactions those have the
significant impact on the reactivity of the mixtures based on these two
mechanisms were different at low temperature. The sensitivity co­
efficients of the identical reactions based on the NUIG mechanism were
about 1.5 times greater than those based on the merged LLNL mecha­
nism which implies the higher discrepancies in the IDT prediction using
the NUIG mechanism compared with the merged LLNL mechanism as
shown in Fig. 9.
As a whole, the merged LLNL mechanism is more reactive than the
NUIG mechanism and therefore the predicted IDTs from the merged
LLNL mechanism are closer to the measurements. Considering the
overall better performance of the merged LLNL mechanism than the
NUIG mechanism, modifications were carried out to improve the per­
formance of the merged LLNL mechanism for intermediate
temperatures. Fig. 10. Normalized sensitivity coefficients at the IDT for Mixture 7 (TUBS-MN
Sensitivity analysis for mixture 7 that shows more differences be­ 73.3) at 20 bar, 911 and 987 K, and ϕ = 0.4 based on the merged
tween the experimental results and the simulation was first performed to LLNL mechanism.
investigate which elementary reactions have the highest impacts on the
IDT. Fig. 10 depicts the sensitivity coefficients at the IDT for Mixture 7 20 bar but two different temperatures at the RCM experiments
(TUBS-MN 73.3) at 20 bar, ϕ = 0.4, and 911 and 987 K based on the conditions.
merged LLNL mechanism. In this figure, the sensitivity coefficients were As can be seen, “2OH( +M) ↔ H2 O2 ( + M)” reaction has the most
normalized to + 1 or − 1 with respect to the largest absolute value within promoting effect on the ignition at both temperatures, while this effect is
the sensitivity vector, illustrating which reactions play key roles in the comparably higher at 911 K. The reaction “CH4 + HO2 ↔ CH3 + H2 O2 ”
LNG intermediate temperature reactions. Further analysis revealed that has the third dominating effect at 911 K by enhancing the ignition with
the sensitivity analyses for mixture 7 at the same temperature but two the almost same effect at both temperatures.
different pressures, namely, 900 K and 20 and 40 bar, had the same On the contrary, the reaction “CH3 + HO2 ↔ CH4 + O2 ” has the most
results with different sensitivity coefficients (Fig. S5 in the Supple­ inhibiting effect on the ignition at 987 K but its sensitivity becomes
mentary Material). In fact, the pressure does not affect the sequence of much lower at 911 K. The hindering effect of “2HO2 ↔ H2 O2 + O2 ” re­
the most sensitive reactions, therefore the elementary reactions for action on the ignition at both temperatures are proportionally similar.
modification were selected according to the sensitivity analysis only at This is a duplicate reaction, whereas the mechanism consists of 2

7
S. Nadiri et al. Fuel 302 (2021) 121137

reactions with the same reactants and products but different rate pa­ data for C0 to C9 alkanes.
rameters. Furthermore, “CH3 + HO2 ↔ CH3 O + OH”, “H + O2 ↔ O + GRI-Mech 3.0 was developed by Smith et al. [56] as an optimized
OH” and “2CH3 ( +M) ↔ C2 H6 ( + M)” reactions only being found at mechanism to the previous version by updating some reaction rate
higher temperature but other reactions, namely, “C2 H6 + OH ↔ C2 H5 + constants with the recent kinetic data from literature and optimizing
H2 O”, “CH2 O + CH3 O2 ↔ CH3 O2 H + HCO” and “C3 H8 + them employing new natural gas combustion experiments data carried
CH3 O2 ↔ CH3 O2 H + IC3 H7 ” are more sensitive at 911 K. out in different shock tubes and other facilities to measure the IDT,
It was found that the rate constants of the aforementioned elemen­ laminar flames speeds and species profile.
tary reactions were not up-to-date or numerically determined, which As a result, the substitution of 7 reactions listed in Table 2 made the
leads to higher uncertainty in the studied temperature and pressure performance of the merged LLNL mechanism adequately better.
ranges. Therefore, literature mechanisms from Konnov-2008 [54], Detailed modification is described as follows:
Guzman-2019 [55] and GRI-Mech 3.0 [56] containing those most sen­ The “H + O2 ↔ O + OH” reaction is a chain-branching reaction
sitive reactions were selected to compare the rate constants applied to which is one of the main reactions in combustion. The rate constant
identify the most appropriate one for predicting experimental IDTs. parameters of the R.1 in the merged LLNL mechanism is acquired from
Applying the trial and error method, where the rate constant of the Hessler’s [62] work which is derived theoretically by implementing the
aforementioned sensitive reactions was substituted one by one, the
performance of the merged LLNL mechanism has been comprehensively Table 2
evaluated. Fig. 11 represents a flowchart describing the whole investi­ The rate constant parameters (k) of the selected reactions; k = ATn exp(− E/RT).
gation procedure of the merged LLNL mechanism.
No. Reactions Preferred reaction rate constant Source
The Konnov-2008 mechanism was reported by Konnov et al. [54]
A n E
with the aim of updating the previous mechanism from their group [57]
for the hydrogen combustion. To achieve this, they applied the kinetic R.1 H + O2 ↔ O + OH 2.06E + − 0.097 1.502E Konnov-
data from Baulch et al. [58] which is a compilation of evaluated kinetic 14 +4 2008 [54]
R.2 OH + HO2 ↔ H2 O2 + O 2.800E 0.00 6.40E +
data. The predictive capability of Konnov-2008 mechanism in simu­
+ 13 3
lating ignition delay times of hydrogen oxidation was validated for a R.3 CH3 O2 + CH4 ↔ CH3 + 9.60E-1 3.77 1.781E Guzman-
wide range of temperature and pressure, e.g. 950–2700 K and 1–87 atm CH3 O2 H +4 2019 [55]
in shock tubes. R.4 2OH( +M) ↔ H2 O2 ( + M) 7.40E + − 0.370 0.00 GRI-Mech
The Guzman-2019 mechanism was proposed by Guzman et al. [55] 13 3.0 [56]
R.5 CH4 + OH ↔ CH3 + H2 O 1.0E + 8 1.6 3120
which is a developed mechanism to investigate the oxidation of an iso-
R.6 2CH3 ( +M) ↔ C2 H6 ( + 6.770E − 1.180 654
paraffinic alcohol-to-jet fuel in a low pressure shock tube at a nominal
M) + 16
pressure of 4 bar, and temperature of 900–1550 K. This model is con­
R.7 CH2 O + HO2 ↔ HCO + 5.60E + 2 1.2E + 4
structed hierarchically on the kinetic models of Atef et al. [59], Oehls­ H 2 O2 6
chlaeger et al. [60] and AramcoMech 2.0 [61], containing the kinetic

Fig. 11. The flowchart describing the whole investigation procedure of the merged LLNL mechanism.

8
S. Nadiri et al.
least-squares analysis and using the experimental data from Pirraglia
et al. [63] at temperatures of higher than 1000 K that may lead to poor
agreement for the IDTs measured below 1000 K. The substitution of the
rate constant parameters of this reaction by that given in Konnov-2008
mechanism [54] has a remarkable impact to decrease the simulated
IDTs. The rate constant parameters applied by Konnov and co-workers
were proposed in the kinetic data for combustion modeling by Baulch
et al. [58]. The determination of the expression of k by Baulch and co-
workers for the forward reaction was carried out in a shock tube at
temperatures above 800 K, while the expression of k for the backward
reaction was determined by several experiments in a discharge flow
system for the temperature range of 250–3000 K [58].
In Fig. 10, only the 14 most sensitive reactions were presented
whereas the “H2 O2 + O ↔ OH + HO2 ” reaction is around the 30th most
sensitive reaction among those 3950 reactions, nevertheless, this reac­
tion showed a strong impact on the IDT by doing the brute force analysis.
The rate constant parameters of this reaction in the merged LLNL
mechanism are attained from Tsang and co-worker’s [64] chemical ki­
netic database. Although the rate expression of the forward reaction in
Konnov-2008 mechanism is similar to the Tsang and co-worker’s data­
base and it is in good agreement with the low temperature data, the rate
expression of the backward reaction is different, which rose the reac­
tivity of LNG mixtures combustion in simulation. The reverse rate con­
stants of all reactions in Konnov-2008 mechanism [54] were calculated
by Chemkin from the forward rate constants and thermodynamic data,
which is more reasonable at low to intermediate temperature.
Extensive researches have shown that some carbon-related inter­
mediate species such as CH3O, CH3O2, CH2O, C2H5O, etc. are significant
in the LNG combustion at intermediate temperatures [65]. Petersen
et al. [65] showed that 13 reactions are crucial at intermediate tem­
peratures in the kinetic study of methane oxidation to acquire a better
agreement between the model and experimental data. One of these
important reactions was the reaction between CH3O2 and CH4, which is
the H-atom abstraction by methyldioxydanyl radicals from the methane.
The rate constant parameters calculated by the HJCFIT method [66],
which is a computer program in performing maximum likelihood fitting
of rate constants, were adopted in Guzman-2019 mechanism for the
“CH3 O2 + CH4 ↔ CH3 + CH3 O2 H” reaction. Colquhoun et al. [66]
showed that this method can provide correct estimates of the rate con­
stants. Therefore, utilizing the rate constant calculated precisely by
HJCFIT method is more accurate, especially at intermediate tempera­
ture, than the values adopted in the merged LLNL mechanism based on
the mechanisms of Curran et al. [34,67].
Sensitivity analysis at both temperatures for mixture 7 (Fig. 10)
demonstrates that the most sensitive reaction in enhancing the ignition
is “2OH( +M) ↔ H2 O2 ( + M)”. The value of the reaction rate constant of
this reaction in the merged LLNL mechanism is valid over the temper­
ature range of 1000 to 1500 K [68]. Therefore, applying the rate con­
stant calculated by Zellner et al. [69] and adopted in the GRI-Mech 3.0
[56] improved the merged LLNL kinetic mechanism significantly,
particularly at intermediate temperatures. This rate constant was
measured by using flash photolysis of water vapor at temperatures
higher than 300 K [69]. Also, the third body efficiencies of the GRI-Mech
3.0 are lower than that of the merged LLNL mechanism.
The rate constant of the reaction of OH radicals with CH4 in the
merged LLNL mechanism was estimated by Curran et al. [67], which
was fitted to the NIST database. The rate constant expression reported in
GRI-Mech 3.0 was calculated by Cohen [70]. Cohen determined the
reaction rate constant of “CH4 + OH ↔ CH3 + H2 O” reaction by per­
forming transition state theory (TST) calculations. The TST showed an
excellent agreement with experimental results over the temperature
range of 298 to 1510 K [70].
As shown in Fig. 10, at a compressed temperature of 987 K and
pressure of 20 bar, the recombination of methyl radicals in the presence
of different inert gas is one of the most sensitive reaction in hindering the
ignition. The rate constant adopted in merged LLNL mechanism was
9
Fuel 302 (2021) 121137
obtained by Walter et al. [71] by carrying out the measurements at 200,
300 and 408 K and low pressures. On the other side, the rate constant
adopted in GRI-Mech 3.0 was calculated by Wagner et al. [72] by
applying a microcanonical variational version of
Rice–Ramsperger–Kassel–Marcus (RRKM) theory at high pressure [73].
Although the value of the rate constant calculated by Wagner and co-
worker is valid over the temperature range of room temperature to
2000 K, it showed higher accuracy at temperatures below 1000 K.
The sensitivity analysis of mixture 7 at both 911 and 987 K shows
that the reactions of HO2 radicals with formaldehyde enhances the
ignition considerably. The rate constant expression of “CH2 O +
HO2 ↔ HCO + H2 O2 ” reaction was studied in a shock tube over the
temperatures of 1340 to 2270 K and pressures of 0.7 to 2.5 atm by
Eiteneer et al. [74], whereas this expression is adopted in the merged
LLNL mechanism. In the GRI-Mech 3.0 mechanism, which is an opti­
mized mechanism to version 2.11, the rate constant of this reaction was
initially adopted from both Eiteneer et al. [74] and Hidaka et al. [75] for
the temperatures from 1150 to 1900 K and pressures from 1.4 to 2.5 atm.
The final reported rate constant expression in the GRI-Mech 3.0 mech­
anism can predict the experimental data at lower temperatures, namely
773 K and 541–565 K [76,77], and higher temperatures from 1250 to
1600 K, acceptably. Since the rate constant expression given in the
merged LLNL mechanism could not reproduce the measurements at
lower temperatures, the expression was optimized by GRI-Mech 3.0 to
fit the high and low temperatures as illustrated in Table 2.
Additionally, since the thermochemical properties of the species
must correspond to the updated rate constants, the thermochemical
properties of the 5 intermediate species, namely, O2, HO2, H2O2, CH3,
C2H6 were updated based on Guzman et al. [55] database adopted from
the latest group values of Burke et al. [78]. Burke and co-workers [78]
employed the group additivity approach of Benson to obtain the most
precise thermochemical data for C1-C4 species and the related species
and radicals, by adopting new groups of molecules and optimizing the
group’s thermochemical values. The new mechanism, namely
LLNL_Modified, contains in total 497 species and 3945 reactions after
the modifications, and the detailed mechanism as well as the thermo­
dynamics data can be found in the Supplementary Material.
4.2. HPST results
The newly developed mechanism was validated first against the
measured IDTs obtained in both HPST and RCM. The results obtained
from the modeling of HPST at 10 and 20 bar, and equivalence ratios of
0.4 and 1.2, and the temperature range of 1090–1555 K are summarized
in four main groups based on the pressure and equivalence ratio,
whereas for each specific pressure and equivalence ratio combination
(P/ϕ) the mixtures were categorized according to the methane number
(MN).
Figs. 12–15 depict the comparison between simulations and experi­
mental results for the P/ϕ group 10 bar/0.4, 20 bar/0.4, 10 bar/1.2, and
20 bar/1.2, respectively. In general, the modified LLNL mechanism
predicts the experimental trends precisely at all studied conditions. In
Fig. 12A, the mixture 1–4 that contain completely different composi­
tions are plotted together due to the equal MWM-MN.
According to the experiments, mixture 4 composed of mostly CH4
and 3% C4H10 isomers without any C2H6 and C3H8, is more reactive than
those three mixtures constituted of mostly CH4, and C2H6 and C3H8 (all
four mixtures are constituted of equal amount of N2). Previously, Shu
et al. [31] demonstrated that LNG mixture containing more ethane is
more reactive if the MWM-MN is identical. However, substitution of
C2H6 and C3H8 with C4H10 isomers with the same MWM-MN even in­
creases the reactivity of the mixture that might lead to a higher knocking
propensity in engine operations.
This uncorrelation between MWM-MN and IDT can be solved by
applying the TUBS-MN which shows that mixture 4 has a clearly lower
MN than mixture 1–3, which are close to each other. This leads to
S. Nadiri et al.
Fig. 12. IDTs of LNG mixtures measured in the HPST at 10 bar, ϕ = 0.4. A) Mixtures 1–3 [31] and 4, B) Mixtures 7 [31], 5 and 6, C) Mixture 9 [31], D) Mixtures 12
[31], 11 and 13 , E) Mixture 16 [31], F) Reference mixtures [31]. (Symbols: experimental points; Lines: model predictions).
shorter IDTs of mixture 4 than other 3 mixtures, and this trend has been
well predicted by the LLNL-modified mechanism. The change of gas
composition by introducing different butane and pentane isomers has
been well captured by the LLNL_modified mechanism as well, and the
minor impact of butane and pentane isomers (Fig. 12B and 12D) can
also be well predicted.
Unlike the 10 bar/0.4 case, the reactivity of mixture 4 is virtually the
same as the mixtures 1–3 at 10 bar and equivalence ratios of 1.2
(Fig. 13A), and the LLNL_modified mechanism can capture this change
very well. This difference can be attributed to the high amount of fuel
available at this equivalence ratio, and different gas composition may
not affect the ignition process. To investigate this effect, a sensitivity
analysis has been performed to compare the key reactions for the igni­
tion at both equivalence ratios for mixtures 2 and 4, which are given in
the following section (3.5).
Another important finding in simulation of the ignitions was that the
LLNL_modified mechanism shows a good agreement with the reference
mixtures employing the equivalence ratio of 0.4, pressures at 10 and 20
bar, and temperatures between 1090 and 1425 K (Figs. 12F and 14D).
The model confirms the fact that increasing the methane amount in the
mixture decreases the reactivity of the mixtures and a mixture with a
lower amount of methane ignites faster.
10
Fuel 302 (2021) 121137
Both measurement and modeling results in Fig. 14A show that the
IDTs of mixture 1–3 at 20 bar, equivalence ratio of 0.4 and temperatures
between 1105 and 1525 K are almost equivalent to lower temperatures.
At higher temperatures (>1300 K), a significant differences were
observed in IDTs of the three mixtures, whereas the model predicts a
similar divergent trend as well. These kinds of discrepancies were not
observed in the modeling of the IDTs of mixture 1–3 at 20 bar, equiv­
alence ratio of 1.2, and the mixtures depict a similar IDT at each tem­
perature with the similar trend (Fig. 15).
No significant differences in reactivity were observed in mixtures
with MWM-MN of 73 and 76 at 20 bar, similar to the observation at 10
bar. This does not agree to the results observed by Gersen et al. [79] in
the investigation of knock resistance of LNG mixtures with different
compositions, where higher amount of C4 isomers have been applied.
Therefore, a sensitivity analysis has been performed to investigate the
impact of isomers on the IDTs (Section 3.5).
Another important finding in the simulation of the ignitions was that
the model employing the LLNL_modified mechanism shows a good
agreement with the experimental results of reference mixtures at
equivalence ratio of 0.4, pressures of 10 and 20 bar, and temperatures
between 1090 and 1425 K (Figs. 12F and 14D). The model proves the
fact that increasing the methane amount in the mixture decreases the
S. Nadiri et al. Fuel 302 (2021) 121137

Fig. 13. IDTs of LNG mixtures measured in the HPST at 10 bar, ϕ = 1.2. A) Mixtures 1–3 [31] and 4, B) Mixtures 7 [31], 5 and 6, C) Mixtures 12 [31], 11 and 13.
(Symbols: experimental points; Lines: model predictions).

Fig. 14. IDTs of LNG mixtures measured in the HPST at 20 bar, ϕ = 0.4. A) Mixtures 1–3 [31], B) Mixtures 7 [31], 5 and 6, C) Mixtures 12 [31], 11 and 13, D)
Reference mixtures [31]. (Symbols: experimental points; Lines: model predictions).

11
S. Nadiri et al.
Fig. 15. IDTs of LNG mixtures 1–3 [31] measured in the HPST at 20, ϕ = 1.2.
(Symbols: experimental points; Lines: model predictions).
Fig. 16. IDTs of LNG mixtures measured in the RCM at 20 and 40 bar, ϕ = 0.4. A) Mixture 7, B) Mixtures 8–10 [31], C) Mixture 12 , D) Mixture 14–16 [31], E)
Reference mixtures. (Symbols: experimental points; Lines: model predictions).
12
Fuel 302 (2021) 121137
reactivity of the mixtures, and a mixture with a lower amount of
methane ignites faster.
4.3. RCM results
As shown in Fig. 9, the merged LLNL mechanism predicted overall
longer IDTs than the measurements at low to intermediate temperatures
and high pressures, especially at 40 bar. Comparisons between the
ignition delays simulated applying the modified model and the experi­
mental data are depicted in Fig. 16. To prevent an overcrowding of the
figures, in case of 3 mixtures represented in one plot, only the uncer­
tainty of one mixture was shown with error bars considering the fact that
the uncertainty of different mixtures with the identical MN is almost
equal.
As shown in Fig. 16, the modified LLNL mechanism demonstrates
much improved performance in predicting the IDTs of the LNG mixtures
measured in RCM where most simulated results are in line with the
experimental data or within the uncertainty of the measurements, e.g.,
mixture 7 as the “worst case”. In Fig. 16B and D, the measured IDTs of
S. Nadiri et al.
mixtures 8–10 and mixtures 14–16 taken from Shu et al. [31] demon­
strates that the changes in butane and pentane isomers in the LNG
mixtures have negligible impact on the ignition delays at low to inter­
mediate temperatures, which is consistent to the finding of the shock
tube investigation (Fig. 12). This phenomenon has been well captured
applying the LLNL_modified mechanism. In addition, the model based
on the developed mechanism provided appropriate predictions for the
reference mixtures 50, 70 and 90 at 20 bar, equivalence ratios of 0.4, and
temperature from 920 to 1035 K.
4.4. Further validation of the mechanism
To assess the modified mechanism further, the IDTs measurements of
methane/n-Butane oxidation in air at high pressures and temperatures
from 660 K to 1330 K performed by Healy et al. [80] were utilized. The
measurements were carried out in a rapid compression machine and a
shock tube from fuel-lean to fuel-rich conditions.
The experimental data available in their Supplementary Material
were used to calculate the IDTs using the LLNL_modified mechanism.
Without access to the pressure profiles of each measurement, the IDTs
calculations were performed using reported TC and PC for RCM and T5
and P5 for ST to define the mixtures and create an ideal gas reactor
subsequently. Therefore, the IDT in ST without creating a volume profile
is defined as the time when the dp/dt is maximum. Fig. 17 depicts that
the model predicts the IDTs trends for both blends of 90% CH4/ 10% n-
C4H10 and 70% CH4/ 30% n-C4H10 with different equivalence ratios at
1190 to 1460 K very well.
As discussed before, heat losses must be considered when simulating
RCM experiments. Thus, the pressure profiles from the non-reactive
experiments were utilized to create the volume profiles. Fig. 18 de­
picts a comparison between measured and simulated IDTs of mixture 12
with and without application of the volume profiles. Similar to the ST
simulation, the IDTs without volume profiles were determined at the
time of maximum dp/dt.
Fig. 18 reveals clearly that there has been a gradual increase from
higher temperatures to the lower temperatures at both pressures. It
postulates the fact that in an ideal condition without any heat losses the
reactivity of the mixture is predicted much higher than the reality.
The simulation of the RCM measurements from Healy et al. [80] at
30 atm and ϕ = 0.35, and 10 and 20 atm, ϕ = 1.16 from 700 to 965 K
were performed applying constant volume constraints without creating
any volume profiles due to the lack of the raw data from Healy et al.
[80]. Fig. 19 demonstrates an overall good agreement between mea­
surements and simulations where the simulated IDTs are generally
shorter than the experimental data. This discrepancy is attributed to the
Fig. 17. IDTs of different methane/n-Butane blends oxidation measured in a
shock tube by Healy et al. [80] at 10 atm, ϕ = 0.32, 1.07, and 2.31. (Symbols:
experimental points; Lines: model predictions).
13
Fuel 302 (2021) 121137
Fig. 18. Comparison of the model predictions for ignition of mixture 12 [31]
(TUBS-MN 76.4) in the RCM at 20 and 40 bar, and ϕ = 0.4. (Symbols: exper­
imental points; Lines: model predictions).
missing information of the heat loss, considering the heat loss effect
showed in Fig. 18, the model can be expected to predict those data very
well.
4.5. Correlation between IDTs and MNs
In this section, the correlation between the simulated IDTs based on
the LLNL_modified mechanism and MNs at 800 and 1200 K, pressure of
40 bar, and stoichiometric air–fuel ratio, implying the operation con­
ditions of modern LNG engines, was investigated. Both MWM- and
TUBS-MN methods were chosen to make a comparison. As can be seen in
Fig. 20, mixtures with lower MN indicating more reactivity than the
mixtures with higher MN, and the LNG mixtures with the same MNs
based on the MWM algorithm but slightly different TUBS-MNs, do not
have the exact same IDTs.
This figure demonstrates that the TUBS-MN method, which consider
the butane and pentane isomers separately, is more precise than the
MWM-MN method, and these isomers have different impact on the
reactivity of the LNG mixtures. These discrepancies in the IDTs of the
LNG mixtures within each MWM-MN category are more obvious at 800
K compared with those at 1200 K. Moreover, as illustrated in Table 1, the
mixtures with MWM-MN of 80 (mixtures 1–4 represented in red color)
have different TUBS-MNs due to their different composition, therefore
mixture 4 with lower TUBS-MN (near 74 instead of 80) shows higher
reactivity than other mixtures (1–3) of this category. This implies that
the TUBS-MN can be more precise than the MWM-MN at low to inter­
mediate temperatures.
4.6. Kinetic modeling investigations
As illustrated previously, all the investigated LNG mixtures have
been categorized via MNs. In the same MN group, the gas compositions
are differed to each other. The measurements showed an inconsistent
correlation between IDTs and MNs, therefore modeling investigations
were further carried out to analyze the chemistry behind. As shown in
Fig. 12A, mixture 2 and 4 show different IDTs in the same temperature
range while both mixtures have identical MWM-MN 80. To better un­
derstand the most important elementary reactions that influence the
ignition kinetics of mixtures 2 and 4 at both fuel-lean and fuel-rich
conditions, the sensitivity analyses were carried out at 1300 K and 10
bar (Fig. 21).
Fig. 21 depicts that at lean-fuel condition, the sensitivity coefficients
of the same elementary reactions that influence the ignition event of
mixture 2 are different from that of mixture 4. The reactions “CH3 +
HO2 ↔ CH4 + O2 ” and “2CH3 ( +M) ↔ C2 H6 ( + M)” are a good
S. Nadiri et al. Fuel 302 (2021) 121137

Fig. 19. IDTs of methane/n-Butane blends oxidation measured in a rapid compression machine by Healy et al. [80] at A)30 atm and ϕ = 0.35, B) 10 and 20 atm, ϕ =
1.16. (Symbols: experimental points; Lines: model predictions).

Fig. 20. Correlation between IDTs and MNs from MWM and TUBS algorithm of LNG mixtures at 40 bar, ϕ = 1 and A) 1200 K, B) 800 K.

illustration of this discrepancy, whereas the sensitivity coefficients of

Fig. 21. Sensitivity coefficients at the IDT at 10 bar, and 1300 K for mixture 2
and mixture 4, A) ϕ = 0.4 and B) ϕ = 1.2 based on the LLNL_Modi­
fied mechanism.
these reactions for mixture 4 are higher than that of mixture 2. More­
over, due to the presence of 10% C2H6 in mixture 2, the abstraction
reactions between C2H6 and OH radical, and between C2H6 and the CH3
radical, play a key role in enhancing the ignition event of mixture 2.
Therefore, these differences in the most sensitive elementary reactions
result from the difference between the IDT of mixture 2 and 4.
On the other hand, the sensitivity analysis at fuel-rich conditions
show nearly identical reactions with approximately the same sensitivity
coefficients at the IDTs of mixtures 2 and 4 which is consistent with the
similarity of the IDTs of both mixtures. These approximate equalities can
refer to the presence of an excessive ratio of fuel to the oxygen that
provides a higher amount of methane to be consumed by oxygen, and
the elementary reactions related to the methane and methyl radical have
the most significant influence on the ignition event of both mixtures.
As shown previously, to investigate the effect of different molecular
structures of butane and pentane, two categories of mixtures, including
3 mixtures with the MWM-MN of 73 and 76, respectively, were studied.
The MWM method cannot discriminate between isomers of butane or
pentane, but the MNs of mixtures 5–7 and 11–13 based on the TUBS
method were slightly different due to the ability of this method to
consider C4 and C5 isomers.
However, both experimental results and the model show equal
reactivity for all three mixtures of each mentioned category at 10 and 20
bar and ϕ = 0.4 and 1.2. Therefore, the sensitivity analysis has been
performed for mixtures 5–7 and mixtures 11–13 at 10 bar, ϕ = 0.4 and
1300 K, to have a deeper insight into the elementary reactions that have
effect on the ignition of these mixtures.
Fig. 22 and Fig. 23 show the sensitivity coefficients of 10 most
important elementary reactions, whereas the reactions and the corre­
sponding coefficients for the mixtures of each category are nearly

14
S. Nadiri et al. Fuel 302 (2021) 121137

Fig. 22. Sensitivity coefficients at the IDT at 10 bar, ϕ = 0.4, and 1300 K for
mixture 5, mixture 6, and mixture 7 based on the LLNL_Modified mechanism.
Fig. 24. Comparison of the IDTs of LNG mixtures and reference mixtures
measured in the RCM at 20 bar, ϕ = 0.4. (Points are experimental data and lines
are linear fits.) [81]

To understand this phenomenon and investigate the chemistry of

ignition to get deeper insights into the vital reactions controlling the
ignition kinetics of the mixtures, the sensitivity analyses for mixture 9
and reference mixture at exactly the same conditions namely 20 bar, ϕ
= 0.4 and 985 K were carried out (Fig. 25). Since the MN of mixture 9,
based on TUBS method, is 67.8, the sensitivity analyses for the reference
mixture were performed with the composition of 67.8% methane and
32.2% hydrogen to have a more precise comparison.
As shown in Fig. 25 is, the chain branching reaction “CH3 + HO2 ↔
CH4 + O2” and “2OH (+M) ↔ H2O2 (+M)” reaction show comparable
influence in hindering and enhancing the ignition events of both mix­
tures, respectively, but other sensitive reactions influencing the IDTs are
not similar. For example, the sensitivity coefficient of the chain termi­
Fig. 23. Sensitivity coefficients at the IDT at 10 bar, ϕ = 0.4, and 1300 K for
nation reaction “H + O2 (+M) ↔ HO2 (+M)”, which is the second most
mixture 11, mixture 12, and mixture 13 based on the LLNL_Modi­
fied mechanism. important reaction in increasing the IDT of reference mixture 67.8, is
almost 5 times larger than that of mixture 9. On the other hand, the
chain branching reaction “H + O2 ↔ O + OH” with the negative sen­
identical. This outcome is contrary to that of Gersen et al. [79] who
sitive coefficient that enhances the ignition event has a different influ­
showed that the knock-limited spark timing (KLST) as indicator of the
ence on the IDTs of the mixtures with the 3 times higher impact on the
knock resistance of the mixture containing CH4 and iC4H10 is higher
reference mixture 67.8. The sensitive carbon-related species reactions
than that of the mixture containing CH4 and nC4H10. A possible expla­
are different as well, and for “CH4 + OH ↔ CH3 + H2O” and “CH3 +
nation for this might be that the amount of butane isomers in the mix­
H2O2 ↔ CH4 + HO2” the sensitive coefficient values are different.
tures of their studies is about 6%, while the amount in this study is 1%
Moreover, the fourth most sensitive reaction in decreasing the IDT of
for mixtures 5–7 that contain butane isomers and 0.2% for mixtures
reference mixture 67.8 is “H2 + HO2 ↔ H + H2O2” while the ignition of
11–13 that contain pentane isomers. Thus, this low quantity of isomers
mixture 9 is not sensitive to this reaction.
in the mixtures cannot influence the chemistry of the ignition event
Since by decreasing the temperature the differences between the IDT
considerably. This assumption demonstrates well that neither of the C4-
of an LNG mixture and a reference mixture increases, the sensitivity
and C5-related reactions play an important role in the ignition delay.
analyses were performed for the previous mixtures at 20 bar, ϕ = 0.4
Shu et al. [81] compared the IDTs of LNG mixtures and reference
mixtures measured in the HPST at 20 bar, ϕ = 0.4 and 1170–1450 K and
concluded that the activation energy of LNG is different from that of the
reference mixtures. In this work, the comparison of the activation energy
of the LNG and reference mixtures was extended to 20 bar, ϕ = 0.4 and
900–1050 K as shown in Fig. 24. The figure clearly displays that as the
MN of the LNG and reference mixtures are decreased, the measured IDT
is reduced, and the activation energy of the reference mixtures shows
remarkably different trends, whereas they are unexpectedly dissimilar
to that of the LNG mixtures.
Moreover, the correlation between the MN and IDT of reference
gases and LNG mixtures are not the same, i.e., at temperature > 980 K,
the IDT of LNG mixtures having MN 70–80 are between reference
mixture 50 and 70, and at temperature < 980 K, the reference mixture
shows much longer IDTs than the LNG mixtures. Considering a similar
problem found in ST measurement, this implies that methane/hydrogen
mixtures cannot be applied to quantify the MN of real LNG mixtures, at Fig. 25. Sensitivity coefficients at the IDT at 20 bar, ϕ = 0.4, and 985 K for
least in the manner of IDT. reference mixture 67.8 and mixture 9 based on the LLNL_Modified mechanism.

15
S. Nadiri et al.
Fig. 26. Sensitivity coefficients at the IDT at 20 bar, ϕ = 0.4, and 900 K for
reference mixture 67.8 and mixture 9 based on the LLNL_Modified mechanism.
and 900 K. Fig. 26 illustrates that the sensitivity coefficient of “2OH
(+M) ↔ H2O2 (+M)” and “CH2O + HO2 ↔ H2O2 + HCO”, which in­
crease the reactivity of the mixtures, and “2HO2 ↔ H2O2 + O2” and
“CH2O + HO2 ↔ H2O2 + HCO”, which decrease the reactivity of mix­
tures, are nearly close for both mixtures but there are still some notable
differences between the sensitivity of the ignition of these mixtures. For
instance, the reactions “H + O2 (+M) ↔ HO2 (+M)” and “H2 + HO2 ↔
H + H2O2”, which rise and reduce the reactivity of mixture 9, respec­
tively, do not have influence on the reactivity of reference mixture 67.8.
On the other hand, the sensitivity coefficients of two dominant reactions
in enhancing the reactivity of the mixture 9, namely the reactions of
hydroperoxyl radical with butane and with ethane, are zero for refer­
ence mixture 67.8. As mentioned earlier, the reference mixture 67.8
only contains methane and hydrogen, but 8% of mixture 9 consist of
butane and ethane, therefore, the reactions of butane and ethane with
hydroperoxyl radical are more likely to take place during the auto­
ignition of mixture 9. Taken together, the chemistry of reactions at the
time of ignition for both mixtures illustrates the larger difference be­
tween the IDT of the reference mixture 67.8 and mixture 9 at lower
temperature.
Moreover, Fig. 24 represents the slope of the IDT in terms of 1000/T,
which shows the activation energy of LNG, is similar for all mixtures.
One reason for this is that all mixtures are mainly composed of methane,
which makes the most sensitive reactions similar. But for reference
mixtures it is different. The activation energy of reference mixtures
changes from reference mixture 50 to reference mixture 90 due to the
stronger changes in the composition of mixtures, from 50% CH4 and
50% H2 for reference mixture 50 to 90% CH4 and 10% H2 for reference
mixture 90. Fig. 27 shows the sensitivity coefficients of the most
important elementary reactions at 20 bar, ϕ = 0.4, and 980 K for
reference mixtures 50 and 90. This figure depicts that the values of the
sensitivity coefficients of carbon-related reactions for reference mixture
90 are higher than for reference mixture 50, since the reference mixture
is composed of a higher amount of methane. Inversely, the values of the
sensitivity coefficients of hydrogen-based reactions for reference
mixture 50 are higher than for reference mixture 90, due to the presence
of 50% hydrogen in reference mixture 50. In conclusion, the differences
in the activation energy of the reference mixtures are attributed to the
different types of the most sensitive reactions that strongly depend on
the composition of the mixtures.
5. Conclusion
The purpose of the current study was to develop a chemical kinetic
mechanism for LNG combustion at low-temperature conditions which is
applicable for lean and rich fuel–air mixtures. In the present work, the
data related to the autoignition study of 11 different LNG mixtures and 5
reference mixtures from Shu and co-workers’ [31] measurements were
16
Fuel 302 (2021) 121137
Fig. 27. Sensitivity coefficients at the IDT at 20 bar, ϕ = 0.4, and 980 K for A)
Reference mixture 50, B) Reference mixture 90 based on the LLNL_Modi­
fied mechanism.
evaluated, while the ignition of 5 additional LNG mixtures were
measured in a HPST and a RCM. Both LLNL and NUIG mechanisms were
not able to reproduce the measurements in RCM conditions satisfacto­
rily. Therefore, the merged LLNL mechanism [32,33,37] which had
better performance than the other is modified in this work, taking into
account recently evaluated kinetic data for combustion at intermediate
temperatures and high pressures.
The LLNL_modified mechanism that has an improved performance
provides adequate predictions for the ignition of all LNG and reference
mixtures in both RCM and shock tube conditions, as well as the literature
data of binary natural gas mixtures. Furthermore, the sensitivity ana­
lyses based on the model prove that applying different isomers of butane
or pentane in the mixtures does not affect the reactivity of the mixtures
because their compositions are rather small.
The correlation between IDTs and MN, which was determined based
on the TUBS algorithm were also investigated. This correlation may be
helpful to predict the unknown MN of other LNG fuels. The model
proved that increasing the methane amount in the mixtures reduces the
reactivity of the mixtures that leads to a higher IDT. The comparison of
the IDTs of LNG mixtures and reference mixtures showed that the acti­
vation energy of LNG mixtures is nearly identical, while each reference
mixtures has a different activation energy from other reference mixtures
and the LNG mixtures. The sensitivity analyses illustrated that the most
dominating elementary reactions for the ignition delay are different
between reference and LNG gases. The representative of the ignition
properties of LNGs, e.g., knocking tendency, by applying methane/
hydrogen mixtures needs further investigation.
A limitation of this study is that the production of soot or NOx cannot
be simulated with the LLNL_modified mechanism. Notwithstanding this
limitation, further modeling and experimental work should be con­
ducted to reduce this comprehensive reaction kinetics mechanism
because of the huge size of it, which will lead to very expensive
simulations.
CRediT authorship contribution statement
Solmaz Nadiri: Conceptualization, Methodology, Software, Writing
- original draft, Investigation, Validation, Formal analysis. Sumit
Agarwal: Resources, Writing - original draft. Xiaoyu He: Resources,
Writing - review & editing. Ulf Kühne: Data curation. Ravi Fernandes:
Supervision, Funding acquisition, Writing - review & editing. Bo Shu:
Conceptualization, Project administration, Visualization, Supervision,
Writing - review & editing.
S. Nadiri et al.
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.
Acknowledgements
This work was part of the EMPIR project 16ENG09 Metrological
support for LNG and LBG as transport fuel (LNG III). The EMRP and
EMPIR are jointly funded by the participating countries within EUR­
AMET and the European Union. The author (Sumit Agarwal) also ac­
knowledges the funding provided by the Alexander von Humboldt
(AvH) Foundation for proving the fellowship grant.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.121137.
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