Fuel 293 (2021) 120388

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Fuel
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Full Length Article

Development of a reduced multi-component combustion mechanism for a

diesel/natural gas dual fuel engine by cross-reaction analysis
Zhenting Liu a, Liping Yang a, *, Enzhe Song a, Jiaqi Wang a, Ali Zare b, Timothy A. Bodisco b,
Richard J. Brown c
a
College of Power and Energy Engineering, Harbin Engineering University, Harbin, China
b
School of Engineering, Deakin University, VIC 3216, Australia
c
Biofuel Engine Research Facility, Queensland University of Technology, QLD 4000, Australia

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

Keywords: In this paper, a four-component reduced mechanism (methane, n-dodecane, methylcyclohexane and toluene)
Natural gas with 150 species and 847 reactions was proposed for predicting the combustion characteristics and emissions
Dual fuel engine from natural gas-diesel dual fuel engines. Equivalence ratio (ϕ) from 0.5 to 2.0, pressure (P) from 30 to 90 bar,
Combustion
temperature (T) from 500 to 1700 K and ϕ from 0.5 to 2.0, P from 1 to 10 bar, T from 298 to 550 K were set as the
Reduced mechanism
Cross-reactions
reaction conditions for two reaction models respectively. The detailed mechanisms were reduced using the
directed relation graphs (DRG), directed relation graphs with error propagation (DRGEP) and full species
sensitivity analysis (FSSA) methods. The validation of the reduced mechanism was performed based on the
ignition delay and the laminar flame speed data available in the literature. Then the effects of cross-reactions on
the oxidation of diesel were further studied, associated with the reaction flux, concentration and sensitivity
analysis. Finally, the reduced mechanisms were verified at a reactivity controlled compression ignition (RCCI)
combustion mode at 25% and 75% loads, the maximum validation error is 3.3%. It was found that the effects of
cross-reactions on ignition were more pronounced in medium and low temperatures. Ignition was also enhanced
by an increase in the equivalence ratio, but was not found to be sensitive to pressure. Under lower temperatures,
adding cross-reactions can better reveal the formation of diesel intermediates. However, at higher temperatures,
the addition of cross-reactions did not significantly increase the reaction speeds of the intermediate products.

1. Introduction greenhouse gas emissions [8]. In addition, in order to achieve low

With demand for vehicles ever increasing, there is a corresponding
increase in demand for oil based fossil fuels, which are known to cause
severe environmental problems [1–2]. It is, therefore, necessary to
explore alternative fuels. Natural gas (NG) has attracted attention owing
to its abundant reserves and reduced exhaust emissions [3–5]. NG-diesel
dual fuel engines are employed in some heavy-duty vehicles and also in
marine engines because of thermal efficiency and emissions advantages
[6].
Dual fuel engines can produce a reliable output power and higher
efficiency under different engine loads with lower CO2 and particulate
matter (PM), when compared to conventional diesel engines [7]. How­
ever, the slower burning rate of natural gas needs more time for heat
transfer to the end gas, if the NG in the cylinder incompletely burns, the
methane emission will increase, thus significantly increasing
temperature combustion to simultaneously reduce NOx and PM emis­
sions, reactivity controlled compression ignition (RCCI) combustion
mode has been widely studied, higher requirements are put forward for
the understanding of combustion process [9]. Therefore, the key to
being able to improve the efficiency, performance and emissions of dual
fuel engines is a better understanding of the chemistry involved over a
wide range of temperatures and pressures relevant to engine operation.
It is, therefore, important to study the reaction kinetics of combustion
chemistry to solve the main problems of engine combustion [10],
coupling the chemical kinetic mechanism with a computational fluid
dynamics model has also become an important approach.
Some researches have focused on the chemical mechanisms of in­
ternal combustion engines during compression and ignition. Using n-
heptane and methane as the representative species of diesel and NG,
respectively, Aggarwal et al. [11], Maghbouli et al. [12], and Zhao et al.

* Corresponding author.
E-mail address: yangliping302@hrbeu.edu.cn (L. Yang).

https://doi.org/10.1016/j.fuel.2021.120388
Received 16 December 2020; Received in revised form 25 January 2021; Accepted 31 January 2021
Available online 4 March 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
Z. Liu et al.
[13] each developed reduced chemical mechanisms for dual fuel en­
gines. However, all of these approaches used a single component as the
substitute of diesel. Commercial diesel fuel is a mixture of more than 200
components [14]; as such, it is not truly representative to simulate the
combustion process of diesel fuel with a single component. Recognizing
the limitation of single-component diesel surrogate fuel models, it is
necessary to develop surrogate models with matching fuel compositions
to actual diesel fuels. Some researchers have developed multi-
component chemical mechanism models to better represent the com­
bustion process of commercial fuels [15–18]. However, the detailed
chemical reaction mechanism of hydrocarbon fuel always contains a
large number of elemental reactions and components, if a detailed re­
action mechanism is directly coupled with a computational fluid dy­
namics (CFD) model, it will need to consume huge computer resources
[19–20]. Therefore the simplification of complex chemical mechanisms
is an important research direction in the field of fuel combustion.
Using reaction path, sensitivity analysis and slight modification of
thermodynamic data, Zhong et al. [15] developed a chemical kinetic
mechanism consisting of 89 species and 355 elementary reactions which
were composed of five components, namely: iso-octane, n-heptane,
ethanol, toluene and diisobutylene. Model validation results showed
that using the reduced mechanism, the predicted ignition delay times
and laminar flame speeds were consistent with experimental results; not
only for pure mono-component fuels, but also for mixed multi-
component gasoline surrogate fuels and commercial gasoline. Ra and
Reitz [16] developed a reduced chemical kinetic mechanism for the
oxidation of representative surrogate components of a typical multi-
component automotive fuel and the final version of the mechanism
consisted of 113 species and 487 reactions. Poon et al. [17] combined
the reduced mechanisms including n-hexadecane (HXN), 2,2,4,4,6,8,8-
heptamethylnonane (HMN), cyclohexane (CHX) and toluene into two
different versions of multi-component diesel surrogate models. The in­
tegrated mechanisms were then comprehensively validated in zero-
dimensional chemical kinetic simulations under a wide range of condi­
tions. Chang et al. [18] have also formulated a diesel surrogate fuel
model with toluene, n-decane, iso-octane and methylcyclohexane to
represent diesel fuel. The integrated mechanism was comprehensively
validated against the experimental data for each fuel constituent and
blend, as well as for commercial diesel fuel under a wide-range of
operating conditions.
In most of the multi-component chemical mechanism models used in
the literature, a ‘reduced-then-combined’ model construction strategy
was employed. The detailed mechanisms of pure mono-component fuels
were simplified separately after the scale and prediction accuracies were
satisfied. These reduced mechanisms were subsequently combined to
generate the final multi-component surrogate models. However, the
interactions between the pure single-component fuels chosen, known as
cross-reactions, in which free radicals produced by one fuel extract
hydrogen ions from another fuel during the oxidation process have been
neglected, which may affect the prediction accuracy when coupling with
CFD models. Therefore, in order to improve the accuracy of dual fuel
combustion CFD modeling, the effects of cross-reactions should be
considered and analyzed in the mechanism development process.
Based on the above discussion, the main aim of this study is to
develop a reduced multi-component chemical kinetic mechanism to
simulate the combustion characteristics and emissions of dual fuel en­
gines. Firstly, the detailed mechanisms of the diesel and NG species have
been simplified using a directed relation graph (DRG), error propagation
extension to DRG (DRGEP) and full species sensitivity analysis (FSSA).
After the mechanism size was satisfied, the reduced mechanisms were
examined and merged based on the comparison of ignition delay times
and laminar flame speeds (determined with the detailed mechanism and
experimental data available in the literature over a range of equivalence
ratios, temperatures and pressures). In addition, the influence of cross-
reactions between different diesel components was analyzed at
engine-relevant conditions to investigate their effect on the prediction
2
Fuel 293 (2021) 120388
accuracy of combustion. The present work provides foundations for
incorporating realistic chemistry of hydrocarbons into large-scale tur­
bulent or supersonic combustion modeling.
2. Mechanism selection and methodology
2.1. The selection of detailed mechanisms of diesel and NG component
The selection of mechanisms usually follows the following two
principles:
(1) The scale of the mechanism should not be too large, an overly
complex characterization of the fuel can lead to an increase in the
scale of the reaction mechanism and a decrease in its
practicability.
(2) As much as possible, representative fuels with similar physico­
chemical properties as conventional fuels should be selected
[21].
The main components of diesel include alkanes (straight-chain and
branched-chain alkanes), naphthenes, and aromatic hydrocarbons. Even
though the composition of natural gas varies by regions, natural gas is
mainly made up of methane, ethane, propane and butane (methane
accounts for more than 75%). Therefore, three different detailed
mechanisms (n-dodecane, methylcyclohexane and toluene) and a
methane detailed mechanism were selected as the representative com­
ponents of diesel and NG, respectively.
2.2. n-Dodecane mechanism
A detailed n-dodecane mechanism was chosen to represent alkanes
[22]. The detailed kinetic model consists 1306 elementary reactions and
171 species. The base model is USC-Mech II [23] with 111 species and
784 reactions, which describes the oxidation of H2 and CO and the high-
temperature chemistry of C1-C4 hydrocarbons. The model was validated
against experimental data, including fuel pyrolysis in plug flow and jet-
stirred reactors, laminar flame speeds, and ignition delay times behind
reflected shock waves over a wide range of combustion conditions.
2.3. Toluene mechanism
Aromatics are non-negligible components in diesel fuel, which effect
soot formation in the engine combustion process; therefore, toluene was
included to represent aromatic hydrocarbons in this study. Based on the
work of Bounaceur et al. [24], the detailed toluene mechanism contains
329 species and 1888 reactions, which is generated by combining the
rate constants for benzyl radical decomposition from studies by Colket
et al. [25] and Sakai et al. [26], and the addition reaction with a hy­
droxyl radical taken from a study by Hippler et al. [27]. In addition, a
part of the H2/CO and C1 chemistry from a study by Li et al. [28] was
used as the C4 submechanism, C2-C4 chemistry was taken from the work
by Healy et al. [29] and the chemistry of some important unsaturated
species were taken from the work by Laskin et al. [30].
2.4. Methyl cyclohexane mechanism
The methyl cyclohexane mechanism (MCH) employed in this study
[31] is based on the previous work of Pitz et al. [32]. Rate coefficients
were changed based on recent recommendations from the literature to
get better agreements with more experimental data, an additional
concerted elimination pathway important at moderate to low tempera­
tures was also introduced to the resulting chemical mechanism. Exten­
sive validation of the revised kinetic model was performed for flame
speed and concentration of small hydrocarbon species using a wide
range of experimental conditions and data sets [33].
Z. Liu et al.
Fig. 1. Typical relations of the species in the DRG method.
2.5. Methane mechanism
The detailed methane (CH4) mechanism GRI Mech 3.0 [34] with 325
reactions and 53 species, which is one of the most widely used CH4/O2
models to date, was selected in the study. Propane and C2 oxidation
products, new formaldehyde and NO formation, and re-burn targets
have been added. GRI-Mech 3.0 was optimized and validated for
methane and natural gas over a wide range of conditions (1000–2500 K,
10 Torr to 10 atm and ϕ = 0.1–5) based on flame speed measurements
and shock tube experiments [35].
2.6. Simplification method
The basic aim of the mechanism reduction process is to identify
unimportant species and reaction pathways in order to reduce the
complexity of chemistry mechanisms, while still maintaining the
important features over the desired range of operating conditions. Over
the past 20 years, the reduction methods for chemical kinetic mecha­
nisms have been continuously developed; considering the overall size of
the detailed mechanism, DRG, DRGEP and FSSA methods were utilized
in this study.
2.6.1. DRG method
The DRG method [36] identifies unimportant species in a reaction
mechanism by resolving species coupling without any prior knowledge
of the system. Direct species coupling can be defined by the immediate
error to the production rate of a species A, introduced by the removal of
another species B from the mechanism. Such immediate error, noted as
rAB, can be expressed as
∑ ⃒ ⃒
⃒
i=1, I vA,i ωi δBi
⃒ be retained. In this paper, full species sensitivity analysis (FSSA) was
rAB = ∑ ⃒ ⃒ ,
⃒vA,i ωi ⃒ (1)
i=1, I
where
{ (1) Remove each species individually from the smallest skeletal
δBi =
1, if the ith reaction involes species B
(2)
0, otherwise
A and B indicate the species, i indicates the ith reaction of the
mechanism, νA,i indicates the stoichiometric coefficient of species A in
the ith reaction, and ωi is the reaction rate of the ith reaction. The de­
nominator represents the total absolute contributions to the production
rate of species A by all reactions in the mechanism involving species A.
The numerator represents those contributions by reactions involving
species B as shown in Fig. 1.
When the immediate error, rAB, is larger than the specified error-
tolerance level, it means that the removal of species B from the mech­
anism will introduce an error to the production rate of species A.
Therefore, if species A is to be kept in the skeletal mechanism, species B
3
Fuel 293 (2021) 120388
must also be kept to avoid non-negligible error in the concentration of
species A. In addition, if the removal of species C will introduce a sig­
nificant error in species B, retaining species A will also require species C
to be retained in the skeletal mechanism, because of the indirect species
coupling between species A and C. On the other hand, if a species is not
required either directly or indirectly by any species to be retained in the
skeletal mechanism, this species can be safely removed because it will
not introduce any significant error.
2.6.2. DRGEP method
As mentioned above, the DRG can simplify the mechanism by
resolving component coupling without any knowledge of the reaction
system to identify the unimportant components in the reaction mecha­
nism. However, in the standard procedures of DRG, it is assumed that
every species selected to be kept in the mechanism is equally important,
and neglects the connection length between the coupling species. For
example, in Fig. 1, if species A is selected as the starting important
species, species C is recognized as having the same importance as species
B, which competently neglects the longer connection way to reach
species A.
In order to overcome this deficiency, the DRGEP method was
developed based on DRG simplification principle [37]. In the DRGEP
method, once component A is stored in the mechanism, all other com­
ponents that can be obtained from component A through direct and
indirect coupling will be detected using their ‘R value’, which is defined
as:
{ }
RA (B) = max rij , (3)
s
where S is the set of all possible paths from component A to component
B, and rij is the chain product of weights along A given the reaction path.
For example, if A is connected to B by a reaction, and B is connected to C
by a reaction, there is a path from A to C by B, and the R value of that
path is rAB* rBC. According to this definition, if there is at least one
connection path from A to B and its r value is greater than the specified
threshold, component B must be stored in the mechanism. In general,
the DRGEP method can generate skeleton a mechanism with about 10%
less components than the DRG method, further reducing the mechanism
scale [38].
2.6.3. FSSA method
The more complex the kinetic model, the harder it is to identify the
relative importance of each species. To resolve this problem, sensitivity
analysis is usually needed [39]. Sensitivity analysis can help us to better
understand the importance of the chemical processes in the model. This
allows the identification of the pathways that determine the outputs or
products of the model and how sensitive they are to change. If the results
have relatively high sensitivity to a primitive reaction, the reaction will
used as a last resort, when the mechanism could not be reduced further
by any other methods. The FSSA was performed by the following steps:
mechanism generated so far and calculate the induced error on
target parameters for this species.
(2) Rank the species using their induced error in ascending order.
(3) Remove candidate species from the skeletal mechanism accord­
ing to the ranked species and calculate the cumulative induced
error on target parameters after each species is removed. The
process is stopped when the cumulative induced error is beyond
the set threshold.
2.7. Theoretical discussion of cross-reactions
In the combustion process of multi-component fuels, whether there is
cross-reaction between hydrocarbon fuel molecules with different
Z. Liu et al. Fuel 293 (2021) 120388

carbon chain structures has always been controversial. In addition to the Table 1
discussion on the impact of cross-reactions on combustion, researchers Sample points of the closed homogeneous reactor (ϕ = 1).
also have different definitions of cross-reactions in the chemical kinetic Number Pressure Temperature Number Pressure Temperature
mechanism models. There are two kinds of cross-reactions, which can be (bar) (K) (bar) (K)
distinguished from the main components and types of cross-reactions. 1 30 700 13 70 700
The first kind of cross reaction can be defined as the elementary reac­ 2 30 900 14 70 900
tion between the small molecule free radicals (C1-C3 radical or C0 active 3 30 1100 15 70 1100
molecule) generated by oxidation cleavage reaction of a part of the 4 30 1300 16 70 1300
5 30 1500 17 70 1500
macromolecule hydrocarbon structure in multi-component fuel, and 6 30 1700 18 70 1700
between the C0 active molecule and the macromolecule. Because this 7 50 700 19 90 700
kind of reaction usually occurs in the middle and late stage of oxidation 8 50 900 20 90 900
reaction, which has a great influence on the consumption of macro­ 9 50 1100 21 90 1100
10 50 1300 22 90 1300
molecules and the overall combustion, so many scholars have conducted
11 50 1500 23 90 1500
in-depth studies on this reaction process [40,41]. 12 50 1700 24 90 1700
The other kind of cross-reaction is defined as the free radical ex­
change reaction between macromolecules generated by the dehydro­
genation of macromolecules of one component and molecules of another
Table 2
in the multi-component fuel system. Under this definition, typical cross-
Sample points of the laminar flame speed calculator (ϕ = 1).
reactions mainly includes the following three types of reactions:
Number Pressure Temperature Number Pressure Temperature
R1 + R2H ↔ R1H + R2(4) (bar) (K) (bar) (K)

1 1 298 7 5 450
R1OO + R2H → R1OOH + R2(5) 2 1 350 8 5 550
3 1 450 9 10 298
R2OO + R1H → R2OOH + R1(6) 4 1 550 10 10 350
5 5 298 11 10 450
Theoretically, up to half of the fuel consumption rate cannot be 6 5 350 12 10 550
accounted for if such cross-reactions are neglected, so in many pure
component mechanisms, these kinds of cross-reactions are fully
considered. However, studies based on macromolecule active radical shown in Table 1.
cross reactions are very limited, and the influence of the cross reactions Similarly, ϕ from 0.5 to 2.0, P from 1 to 10 bar and T from 298 to
between macromolecules on the combustion process is not yet clear. 550 K were set as the reaction conditions of the laminar flame speed
Thus, the importance of cross-reactions, especially between different calculator. Selecting ϕ as 0.5, 1.0, 2.0, P as 1, 5, 10 bar and T as 298, 350,
diesel components, should be carefully investigated. In this paper, the 450, 550 K, the calculated sampling points (when ϕ = 1.0) are shown in
influence of cross-reactions between different diesel components (n- Table 2.
dodecane, methyl cyclohexane and toluene) is analyzed at engine-
relevant conditions and attempts to explain the influence of cross- 3.2. An introduction of a simplification strategy
reactions on the prediction accuracy of the combustion process and
mechanism model in the process of multi-fuel mixed combustion. In order to achieve better prediction accuracy, and study the inter­
action between the components of diesel during the oxidation combus­
3. Mechanism simplify strategy and development tion process, the DRGEP method was used to efficiently remove
redundant species of the single components, followed by the DRG
3.1. Computational reactor model and reaction conditions method to further remove insignificant reactions and species. The FSSA
method was then applied to delete the rest of the unimportant species.
Flame speed and ignition delay are two important parameters for the After the simplification works were accomplished, the reduced mecha­
evaluation of mechanism model, therefore in the reduction process, they nisms of single components were validated using laminar flame speed
were considered as two mechanism reduction targets, the premixed and ignition time data from the literature. Finally, the reduced mecha­
flame models and closed homogeneous reactor were employed respec­ nisms of single components were merged into the reduced dual fuel
tively in CHEMKIN Pro [42]. The closed homogeneous reactor was mechanism denoted as MODEL I; after the cross-reactions were added to
defined as a closed, adiabatic system ignoring wall effects. The premixed MODEL I, the mechanism was denoted as MODEL II. The concept flow
flame model solves the set of governing differential equations that block diagram of the simplification strategy is shown in Fig. 2.
describe the flame dynamics using implicit finite difference methods, as
well as a combination of time-dependent and steady-state methods,
3.3. Development of reduced multi-component natural gas-diesel
which simulate the propagating burning process.
surrogate fuel models
The target engine of this study is a 6-cylinder, direct-injection,
turbocharged dual fuel engine, with rated power of 309 kW and a
3.3.1. Development of reduced dual fuel mechanism
displacement of 12.2 L. The dual fuel engine adopts RCCI combustion
By analyzing the detailed mechanism, the fuel, oxidizer (O2) and the
mode and can achieve low temperature combustion by changing the
complete combustion products (H2O, CO2, N2) were used as target
activity distribution in the cylinder through two diesel injection pulse.
species to obtain results efficiently, some small molecular products that
Equivalence ratios (ϕ) from 0.5 to 2.0, pressures (P) from 30 to 90 bar
are important to the combustion process were also considered, such as
and combustion temperatures (T) from 500 to 1700 K were set as the
OH. As shown in the mechanism reduction strategy mentioned above,
reaction conditions for the closed homogeneous reactor. In order to
the most important species and reactions associated with the fuel
minimize the calculation time under all working conditions, T was
oxidation process were retained to derive a reduced mechanism. The
selected as an interval of 200 K, P was selected as an interval of 20 bar
comparison of the detailed and reduced mechanisms of the four com­
and ϕ was selected as 0.5, 1.0, 2.0, a total of 6*4*3 = 72 sampling points.
ponents is shown in Table 3:
As the number of selected points is not fully displayed, only sample
As shown in Table 3, we can see that the MCH reduced mechanism
points with an equivalent ratio of 1.0 are selected as an example, as
has the biggest scale, so it was employed as the base mechanism to

4
Z. Liu et al. Fuel 293 (2021) 120388

Fig. 2. Concept flow block diagram of simplify strategy.

Table 3 Table 4
A comparison of the detailed and reduced mechanisms. Comparison of physical and chemical parameters.

Program Species Reactions Program Commercial diesel Blended fuel

Methane Detailed mechanism 53 325 Cetane number 50.9 48

Reduced mechanism 23 82 Molar H/C ratio 1.85 1.89
Liquid density (g/cm3) 0.85 0.776
n-Dodecane Detailed mechanism 175 1318 Low heating value (MJ/kg) 43 43.45
Reduced mechanism 49 265

Methyl cyclohexane Detailed mechanism 369 1896

Reduced mechanism 84 402
Toluene Detailed mechanism 329 1888
Reduced mechanism 61 274
merge with the other three reduced mechanisms. The blending pro­
cedure is time-consuming. If two chemical species have the same
chemical formula, it is necessary to check their thermodynamic data­
bases by comparing the enthalpy, heat capacity, and entropy at several
temperature values. If their thermodynamic properties return the same
(or similar) values, then both chemical species are considered to be
identical and the redundancy removed. The Mechanism Utilities tool of
CHENKIN Pro was employed to complete the mechanism merging pro­
cess, which allows detailed analysis of any overlap and differences be­
tween the mechanism data, to enable informed decisions to be made
during the merge process. After deleting the repeated components and
reactions, the MODEL I mechanism consisted of 150 components and
776 reactions.
After the blending work was accomplished, it was also necessary to
determine the proportions of the three diesel ingredients to match the
physical and chemical parameters of diesel. According to the physico­
chemical parameters of the market diesel fuel shown in Table 4 [43],
using the Surrogate Blend Optimizer (SBO) tool in the CHEMKIN Pro
[42], which is designed to optimize the composition of a model fuel in
order to match specified properties of a commercial diesel fuel, the
ingredient proportions of the three fuels was determined as: 50% for n-
dodecane, 35% for MCH and 15% for toluene (volume fraction). The
comparison of the physical and chemical parameters between the
commercial diesel and the blended fuel from the three species is listed
below. As shown in Table 4, it can be seen that the blended fuel matches
the cetane number and H/C ratio, which are the most important pa­
rameters as they have a significant influence on the flame temperature
and speed, heat of reaction, and emissions.

5
Z. Liu et al.
Fig. 3. Component consumption sensitivity and reaction path analysis of
n-dodecane.
Fig. 4. Component consumption sensitivity and reaction path analysis
of toluene.
3.3.2. Development of reduced dual fuel mechanism with cross-reactions
In the present study, based on the MODEL I mechanism derived from
Section 3.3.1, several cross-reactions between the surrogate components
6
Fuel 293 (2021) 120388
Fig. 5. Component consumption sensitivity and reaction path analysis of MCH.
were considered. It can be seen from the definition of cross-reaction that
the reactants of cross-reactions are mainly secondary products of fuel
components, in order to identify the species related to cross-reactions,
the main intermediate species were analyzed in the oxidation of n-
dodecane, MCH and toluene with the current MODEL I mechanism,
which are shown in Figs. 3–5.
It can be seen that for n-dodecane in Fig. 3, H atom abstraction
products like PXC12H25, SXC12H25 and S2XC12H25 are the most impor­
tant intermediates, some peroxidation products, such as PC12H25O2,
were also considered. For toluene in Fig. 4, benzyl (C6H5CH2), perox­
ybenzoyl (C6H5CHO), phenyl radical (C6H5), benzaldehyde (OC6H4CH3)
and benzene (C6H6) are dominant intermediates. As shown in Fig. 5, the
major hydrocarbon intermediates formed during MCH oxidation
(P = 30 bar, T = 1100 K, ϕ = 1) are four different carbon bond dehy­
drogenation products: MCHR1, MCHR2, MCHR3 and MCHR4, but ac­
cording to the main types of cross-reactions, MCH1OO and CYCHEXCH2
were also added as the intermediates of MCH. Therefore, reactions be­
tween these intermediates were assumed as important cross-reactions in
this study. The chemical structure of the intermediate components is
shown in Appendix file1. According to the previous research work of
Andrae et al. [44,45] and Ra and Reitz [16], a total of 71 cross-reactions
between three diesel components were added in the MODEL I, which is
denoted as MODEL II and consists of 150 species and 847 reactions. All
these added cross-reactions are presented in Appendix file2.
4. Verification and analysis of the reduced mechanism
Validation works were carried out by the CHEMKIN-PRO package for
all of the simulations presented in this section. Ignition delay and flame
speed were selected as the verification objects. Numerous experimental
data from recent fundamental experiments on these two parameters
Z. Liu et al. Fuel 293 (2021) 120388

Fig. 6. Comparison of measured and calculated ignition delay of methane.

Fig. 7. Comparison of measured and calculated flame speed of CH4.

were employed to validate the present surrogate mechanism for each
component.
4.1. Validation of the methane reduced mechanism
For validation of the methane reaction mechanism, several shock
tube studies at engine-like conditions were used [46–49]. Fig. 6 com­
pares the ignition delay of methane simulated with experimental data.
We can see in Fig. 6(a) that at a medium temperature, the predicting
error will slightly increase for the reduced mechanism; in Fig. 6(b) and
(c), both the detailed and reduced mechanisms predict the experimental
data well. Overall, good agreement is achieved between the methane
reduced mechanism and experimental data with respect to ignition
delay over the test conditions.
Fig. 7(a) shows laminar flame speeds of methane-air mixtures, the
experimental data was taken from the research works of Park [50], Gu
[51] and Rozenchan [52]. It can be seen that the flame speed of the CH4
simulated using the reduced mechanism is slightly lower than the
detailed model and measured results. In Fig. 7(b), with the increase of
equivalence and pressure, the prediction accuracy of CH4 reduced
mechanism reduced. Considering measurement errors, rate constant
errors of the kinetic model and some unimportant elementary reactions,

Fig. 8. Comparison of measured and calculated ignition delay of n-dodecane.

7
Z. Liu et al. Fuel 293 (2021) 120388

Fig. 9. Comparison of measured and calculated flame speed of n-dodecane.

Fig. 10. Comparison of measured and calculated ignition delay of toluene.

which may affect the laminar flame generation, on the whole, the
experimental values are in good agreement with current study. More­
over, because NG is predominately burned in the lean-fuel region in a
dual fuel engine, the flame speeds in this region can be well predicted
using the reduced CH4 mechanism.
4.2. Validation of the n-dodecane reduced mechanism
The experimental data of n-dodecane about shock tubes previously
[53–55] were used to evaluate the reduced model. Fig. 8 shows the
comparison between experimental and predicted ignition delay of n-
dodecane. It is seen that although the overall discrepancy is bigger with
an increase of initial pressure, the present mechanism agrees well with

Fig. 11. Comparison of measured and calculated flame speed of toluene.

8
Z. Liu et al.
Fig. 12. Comparison of measured and calculated ignition delay of MCH.
the experimental data. In addition, the mechanism also correctly cap­
tures the complicated negative temperature coefficient (NTC) behavior,
which can be noticed in Fig. 8(b) when ϕ = 1 and P = 80 bar, at tem­
peratures below 950 K.
Fig. 9 illustrates the variation of flame speed for n-dodecane/air, the
experimental data was taken from [56–59]. In Fig. 10(a), the compu­
tational values are lower than Kumar’s [57] data at high equivalence
ratio conditions and the difference becomes larger with an increase in
the initial temperature. However, compared with another data from Ji
et al. [56,58] and Hui [59], at T = 400 K, P = 1 bar, it can be found that
the prediction value is almost the same as the experimental data of Ji
et al. [58]. In Fig. 10(b), the predicted flame speeds are near consistent
with the experimental data in the lean-fuel region, but in the rich-fuel
region, the predicted flame speeds are slightly smaller than the experi­
mental results. Overall, the model accurately follows the dependence of
laminar flame speed on pressure and the simulation results show
excellent agreement with Hui’s data [59]. Flame development in a dual
fuel engine mainly depends on the turbulent intensity, where the
laminar flame speed only has a slight effect [60]. However, the analysis
demonstrates that the reduced model can provide reliable predictions
for laminar flame speed at these conditions.
4.3. Validation of the toluene reduced mechanism
Fig. 10 presents a comparison of the measured ignition delay of
toluene and the corresponding simulation data; the experimental data
Fig. 13. Comparison of measured and calculated flame speed of MCH.
9
Fuel 293 (2021) 120388
was obtained from the shock tube test results of Andrae et al. [61]. The
prediction results fit well with the experimental data, especially in high-
temperature regions. In addition, the NTC phenomenon of toluene in the
medium temperature region can be also be well predicted. Thus, it can
be concluded that the reduced toluene mechanism has good agreement
with the detailed toluene mechanism and measured results.
Fig. 11 shows predictions of laminar flame speeds of toluene using
the detailed and reduced mechanisms compared to the experimental
results [62–68]. In Fig. 11(a), the predicted flame speeds are consistent
with the experimental data except at T = 298 K in the lean-fuel region
and T = 400 K in the rich-fuel region; when T = 470 K the predicted
flame speeds are smaller than the experimental results. However, these
results show an overall matching trend. In Fig. 11(b), it can be seen that
the reduced mechanism slightly over-predicts the flame speed in the
medium-fuel region when P = 2 bar, T = 353 K and P = 3 bar, T = 400 K,
respectively. When P = 3 bar, T = 450 K, although the simulation results
are higher than Lipzig’s data [68] at low and medium equivalence ratio
conditions, compared with the data from Zhong et al. [67], it can be
found that the reduced reaction mechanism is well validated in this
condition.
4.4. Validation of the MCH reduced mechanism
In order to validate the reduced MCH mechanism, the rapid
compression machine (RCM) ignition delay times of a stoichiometric
MCH + O2 + N2 + AR mixture, measured at two different initial
Z. Liu et al.
(a) =0.5 (b) =1
Fig. 14. The valves of δ under different conditions.
pressures by Bryan et al. [69], Gaurav et al. [70] were used in Fig. 12(a).
It can be seen that the verification accuracy of the simplified mechanism
will increase slightly at low temperature, but the maximum error value
is 3.1%, which is still within a reasonable range. The main source of
error is the deletion of some unnecessary low temperature reaction paths
during mechanism simplification, which leads to a slight decrease in the
prediction accuracy of the ignition delay at low temperature. Despite
certain deviations between the simulation results and the experimental
data at P = 50 bar, the NTC phenomenon of MCH in the low-temperature
range is well predicted. Shock tube test data by Subith et al. [71] and
simulated results under 20 bar and 45 bar are illustrated in Fig. 12(b).
Strong agreement between literature data and simulated results can be
noticed both in Fig. 12(a) and (b) at different conditions.
To further test the performance of the present reduced MCH model,
Fig. 13 shows the simulated results and literature data measured over a
wide temperature range from 298 to 450 K, under 1 and 3 bar. It is seen
that all data follow the rule of temperature dependence that at a higher
temperature the flame speed is faster, though slight differences are
observed among the data at the same temperature measured by different
groups in Fig. 13. It can also be noticed that the present data reaches a
peak around the equivalence ratio of 1.1, which is consistent with the
literature [72–75] except for the results from Zhong et al. [67] which
reported the peak value around an equivalence ratio of 1.05 both at 400
and 450 K.
From the above mechanism validations for pure components of NG
and diesel, it can be seen that there are still some discrepancies between
simulation and experimental results. The main reason for this phe­
nomenon is that the simulation of constant energy and volume were not
strictly valid for the experiments of the fuel/air mixtures with long
ignition delay times in shock tubes due to non-ideal facility effects, such
Fig. 15. Reaction rate curves of diesel components.
10
Fuel 293 (2021) 120388
(c) =2
as incident shock attenuation and boundary layer growth [76]. Overall,
all of the ignition behaviors for the pure components were well repro­
duced by the model. The good agreement between the predictions and
the measured ignition delays and flame speeds suggests that the mech­
anisms can capture the ignition behavior for each component in the NG
and diesel surrogate model.
5. The influence of cross-reactions on the oxidation process
5.1. Analysis of the influence of cross-reactions on the ignition delay
To show the effects of cross-reaction on the ignition delay time, two
different mechanisms (MODEL I and MODEL II) were calculated and
compared at different pressures, temperatures and equivalence ratios.
The proportion of diesel fuel mixture involved in the reaction is as fol­
lows: 50% for n-dodecane, 35% for methylcyclohexane and 15% for
toluene (volume fraction). In order to evaluate the differences between
the two mechanism models with respect to ignition delay, the ignition
delay relative deviation, δ, defined by Eq. (7) was used.
δ = (τno cross − τcross )/τno cross *100% (7)
τno cross and τcross are the ignition delay times of the two models with
and without cross-reactions. Fig. 14 compares the values of δ under
different conditions.
It can be seen that with an increase in the initial temperature, the
values of δ generally show a negative trend. The peak relative deviation
occurs at medium and low-temperature conditions (700–900 K), this is
the most pronounced at 900 K. With an increase in pressure, the values
of δ rise slightly; however, owing to the relatively small influence this
has, the effect of initial pressure on the variation of δ during the ignition
Z. Liu et al. Fuel 293 (2021) 120388

Fig. 17. Reaction flux analysis at high temperature (T = 1500 K,

P = 30 bar, ϕ = 2).

Fig. 16. Reaction flux analysis at low temperature (T = 900 K, combustion process; the solid line represents the cross reaction involved,
P = 30 bar, ϕ = 2). and the dashed line does not. It can be seen that the reaction rate keeps
rising with the increase of the initial temperature, the value of the re­
delay period can be neglected. In addition, increasing the equivalence action rate is also improved at high equivalence ratio. In addition, the
ratio will also increase δ, especially at low-temperature conditions. reaction rate growth trend of diesel components will be different under
Based on the conclusion of Fig. 14, Fig. 15 shows the reaction rate the action of cross-reactions. At medium and low temperatures,
curves of diesel components under different temperatures and equiva­ compared to the other two diesel components, the reaction rate of n-
lence ratios. The value of the reaction rate is the maximum value of the dodecane increases significantly under the effect of cross-reactions, as

11
Z. Liu et al.
Fig. 18. Reaction flux analysis when ϕ = 1 (T = 900 K, P = 30 bar).
the temperature further increases, the reaction rate difference under the
model with and without cross-reactions gradually decreases. It can be
seen that the change rule of the reaction rate is consistent with the
change rule of δ in Fig. 14.
5.2. Reaction flux analysis with and without cross-reactions
In order to investigate the behavior of ignition under the reduced
12
Fuel 293 (2021) 120388
mechanism models, taking the maximum reaction rate of diesel com­
ponents, with and without cross-reactions, reaction flux analysis at the
beginning of the reaction was conducted on the two mechanism models
under different initial conditions.
Fig. 16 shows the results of the reaction flux analysis for NC12H26,
MCH and C6H5CH3 under calculation in the closed homogeneous reactor
at low temperatures made with two mechanisms, where A means no
cross-reactions and B means cross-reactions during the combustion
process. As shown in the reaction flux analysis at low temperatures, it
can be concluded that the cross-reactions have a great influence on the
oxidation of the three diesel components at the beginning of the reac­
tion, especially on the consumption of n-dodecane. It can be seen in
Fig. 16(a), for n-dodecane, the important element reactions are basically
the reaction of n-dodecane with OH, H, O and other active components,
the main products were secondary products of PXC12H25, SXC12H25 and
S2XC12H25. With the addition of a cross-reactions, it can be seen that
consumption proportion of PXC12H25, SXC12H25 and S2XC12H25 were
significantly increased, indicating that cross-reactions can accelerate the
component consumption of NC12H26 and was favorable for the further
formation of n-dodecane secondary products. For MCH, the overall ef­
fect of cross-reactions on its consumption is relatively weak, but under
the action of cross-reactions, the consumption ratio of MCHR1 is slightly
increased. Compared with the first two components, the reaction path of
toluene is more complex, as there are both consumption and formation
paths for toluene, the most important reaction path is the reaction of
toluene to C6H5CH2. Under the action of cross-reactions, the reaction
proportion of C6H5CH2 increased by 0.5%, thus the concentration of the
active molecules generated by R584 and R585 increased.
The reaction flux analysis for the three diesel components at high
temperature are shown in Fig. 17. As can be seen from Fig. 17, when the
initial temperature rises to 1500 K, with the action of the cross-reactions,
although the reaction flux values of the three diesel components have a
certain change, for some important secondary products, the increase of
its reaction flux proportion is limited. This shows that the cross-reactions
have a small influence on the consumption process of the three diesel
components under high temperature.
Under the action of cross-reactions, the reaction flux analysis of each
diesel component under the two models when ϕ = 1 is shown in Fig. 18.
Compared with the reaction flux data shown in Fig. 16, it can be seen
that with an increase in equivalence ratio, the difference in the reaction
flux values of the important secondary products will be increased with
and without adding cross-reactions, especially for secondary products
PXC12H25, SXC12H25 and S2XC12H25. The increase in the change value
for the reaction flux means that the role of cross-reactions in the reaction
process also improved with an increase in equivalence ratio, which has
an important influence on the subsequent reaction. Thus, it can be
concluded that with an increase in equivalence ratio, the influence of
cross-reactions on combustion can be promoted.
5.3. Analysis of key components of cross-reactions during combustion
5.3.1. Analysis of diesel intermediate component concentration
In order to further study the influence of cross-reactions, the key
components of cross-reactions on combustion was analyzed through
sensitivity analysis. The first step was to choose the representative in­
termediates of the cross-reactions and small active molecules. As can be
seen from the above reaction flux analysis, S2XC12H25, MCHR2 and
C6H5CH2 all play important roles in reaction path and cross-reactions.
As such, they were selected as representative intermediate compo­
nents of the three diesel components. Fig. 19 shows the mass fraction
curves of the above components with and without cross reactions under
T = 900 K, ϕ = 2, where the solid line shows that there is cross reaction
and the dotted line shows no cross reaction.
As shown below, it can be seen that with the addition of cross re­
actions, the mass fraction curve of each component changes signifi­
cantly. At first, the corresponding times of peak mass fraction of
Z. Liu et al.
Fig. 19. The concentration curves of diesel intermediates (T = 900 K, P = 30 bar, ϕ = 2).
intermediate components are greatly advanced, which is consistent with
the conclusion of Fig. 15. In addition to the increase in the formation
rate of intermediate components, the addition of cross reaction also
caused a certain change in the mass peak value of diesel intermediate
component, indicating that cross reactions would promote the formation
of the intermediate product under low temperature. It can be concluded
from Fig. 16 that the formation process of the intermediate components
is usually accompanied by the formation of certain active components,
so the increase of such intermediate components can promote the
combustion of diesel. In addition, it can be seen that the concentration
curves of the four intermediate components of MCH change greatly with
the addition of cross reaction. When there is no cross-reactions, MCHR1,
MCHR2 and MCHR3 basically presents a gradually increasing tendency
with the reaction time. With the addition of cross reaction, the con­
centration of MCHR1, MCHR2 and MCHR3 first increases rapidly and
reaches the first peak, then drops and comes to the second peak, and
finally rapidly consumes. The difference in this trend was further
explained below. On the whole, cross-reactions effectively improve the
reaction rate and peak mass of diesel component intermediates, thus
promoting the improvement of the basic reaction rate and further fuel
consumption.
In order to further understand the effect of cross reactions on the
subsequent combustion reaction and the reasons for the variation trend
13
Fuel 293 (2021) 120388
of the concentration curve of intermediate products, Fig. 20 shows the
sensitivity analysis of S2XC12H25, MCHR2 and C6H5CH2. As can be seen
from Fig. 20, the reaction R18: H2O2 (+M) = 2OH is positively corre­
lated with the formation of S2XC12H25, MCHR2 and C6H5CH2. As one of
the reactions with the greatest influence on OH generation, the sensi­
tivity coefficients of R18 of the three components are all at a high level,
indicating that the increase of concentration of S2XC12H25, MCHR2 and
C6H5CH2 can effectively accelerate the reaction rate of R18, promote the
generation of OH and thus reduce the ignition delay. In addition, it can
be seen that in the reaction process of diesel, the formation of inter­
mediate components is also accompanied by interactions. In the
S2XC12H25 and C6H5CH2 sensitivity analysis, the reaction R211: MCH-
C7H14 + OH → MCHR3 + H2O is negatively correlated with these com­
ponents. According to the previous analysis, it can be seen that the
growth of these two intermediates has a certain blocking effect on this
reaction, which can also explain the variation trend of MCHR3 con­
centration curve rising first and then falling under the action of cross
reaction in Fig. 19.
5.3.2. Analysis of the concentration of active small molecule components
In view of the results of the above comparative analysis of concen­
tration changes and sensitivity analysis of diesel component in­
termediates under the action of cross reaction, the effects of cross-
Z. Liu et al. Fuel 293 (2021) 120388

Fig. 20. Sensitivity analysis of representative intermediates of diesel components.

Fig. 21. Sensitivity analysis of OH for ϕ = 2, pressure of 30 bar, and temperature of 900 K.

reactions on the concentration change of small active molecules will also analysis of OH, it can be concluded that CH2O, CH2CHO, H2O2, HO2 are
analyzed. Firstly, sensitivity analysis of OH was used to determine the sensitive to the change of OH concentration, so the concentration
small active molecules that need analyze. Fig. 21 shows the sensitivity changes of these four components under models with and without cross

14
Z. Liu et al. Fuel 293 (2021) 120388

most important reaction R18: H2O2 (+M) = 2OH (+M), the OH peak
concentration was also increased. Based on the above analysis, it can be
concluded that cross-reactions can not only promote the consumption of
diesel components at the initial stage of the combustion, but also pro­
mote the rapid formation of active small molecules at the later stage of
combustion, which can effectively accelerate the combustion and
shorten the ignition delay.
The small molecule concentration curves under the two models at
high temperature is shown in Fig. 24. Similar to the reaction flux anal­
ysis shown in Fig. 17, the variation trend of small molecule concentra­
tion is almost the same under the two mechanism models, indicating
that the cross-reactions has very limited influence on the combustion
process of diesel components at high temperature.
Fig. 25 shows the change of the concentration of active molecules
when ϕ = 1. Compared with the concentration curves in Fig. 21, the
relative difference of the peak time of the concentration of small

Fig. 22. Concentration curves of active components (T = 900 K, P = 30 bar,

ϕ = 2; black line: with cross reactions, red line: without cross reactions). (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

reactions will be compared.

The influence of cross-reactions on the change of the concentration
of active molecules under low temperature is shown in Fig. 22. As shown
in the figure, there is a big difference in the curves of active molecules
under the two mechanism models. Firstly, under the action of cross re­
actions, the time when the concentration of small molecules increases
significantly is greatly advanced; secondly, it can be found that the
addition of cross reactions can increase the peak concentrations of H2O2.
According to the H2O2 sensitivity analysis results shown in Fig. 23, the
reactions of SXC12H25 and S2XC12H25 have a positive effect on the for­
Fig. 24. Concentration curves of active components at high temperature
mation of H2O2. It is known by reaction flux analysis that cross-reactions (T = 1500 K, P = 30 bar, ϕ = 2; black line: with cross reactions, red line: without
can increase the reaction consumption proportion of these two compo­ cross reactions). (For interpretation of the references to colour in this figure
nents, so the concentration of H2O2 was increased. Then through the legend, the reader is referred to the web version of this article.)

Fig. 23. Sensitivity analysis of H2O2 for ϕ = 2, pressure of 30 bar, and temperature of 900 K.

15
Z. Liu et al. Fuel 293 (2021) 120388

Table 5
The initial conditions of dual fuel engine.
(a) 25% load

Parameter Value Parameter Value

Speed (rpm) 1134 Torque (N*m) 439

Gas flow (kg/h) 9.47 Inlet flow (kg/h) 414.7
Diesel flow (kg/h) 1.8 Diesel pre-injection ratio (%) 50
Diesel pre-injection timing 25 Diesel main injection timing 10
(◦ CA BTDC) (◦ CA BTDC)

(b) 75% load

Parameter Value Parameter Value

Speed (rpm) 1638 Torque (N*m) 1336

Gas flow per (kg/h) 48.21 Inlet flow (kg/h) 1414.13
Diesel flow (kg/h) 2.32 Diesel pre-injection ratio (%) 50
Diesel pre-injection timing 55 Diesel main injection timing 10
(◦ CA BTDC) (◦ CA BTDC)

Table 6
The temperature boundary conditions of dual fuel engine.
(a) 25% load

Parameter Value (K) Parameter Value (K)

Inlet 310 Cylinder head 400

Gas nozzle 300 Intake port 310
Intake valve 350 Intake valve seat 350
Exhaust valve 490 Combustion chamber 510

(b) 75% load

Parameter Value (K) Parameter Value (K)

Inlet 310 Cylinder head 590

Gas nozzle 300 Intake port 310
Intake valve 455 Intake valve seat 430
Exhaust valve 590 Combustion chamber 585
Fig. 25. Concentration curves of active components when ϕ = 1 (T = 900 K,
P = 30 bar; black line: with cross reactions, red line: without cross reactions).
(For interpretation of the references to colour in this figure legend, the reader is From the above analysis, it can be concluded that under low tem­
referred to the web version of this article.) perature when the overall reaction rate is relatively low, the addition of
cross-reactions better reveals the formation and consumption rate of
intermediate products. From the sensitivity analysis, it is clear that the
accelerated reaction rates of some intermediates promote the formation
and transformation of active molecules such as OH. By contrast, under
higher temperature the overall reaction rate is greatly increased. The
addition of cross-reactions did not significantly promote the consump­
tion rate of intermediates, therefore the ignition delay difference be­
tween the two mechanism models is limited.

5.4. Final comparative verification of MODEL I and MODEL II

In order to further validate the reliability of reduced dual-fuel

mechanism determine the final mechanism for the dual fuel engine,
two mechanism models were coupled into 3D CFD software AVL FIRE
for numerical simulation. Then, the modeled results were compared
with the experimental values. According to the structure of the dual fuel
engine (mentioned in Section 3.1), the CFD model used in this study is
shown in Fig. 26, the adaptive mesh refinement method was applied to
refine the meshes of high temperature and velocity gradient regions with
a minimum cell size of 0.125 mm.

Table 7
The calculation models.
Parameter Model
Fig. 26. Mesh model of dual fuel engine.
Turbulence model k-ζ-f
Diesel droplet decomposition model WAVE
molecules (such as OH) under the two models decreases from 49.75% to Diesel droplet evaporation model Dukowicz
38.74%. So it can be concluded that the effect of cross-reactions on Wall-impingement model Wall
combustion can be promoted with the increase of equivalent ratio. Combustion model General Gas Phase Reaction Module

16
Z. Liu et al.
(a) 25% load
(b) 75% load
Fig. 27. Comparison of simulated in-cylinder HRR and pressure with experi­
mental data.
In the simulation process, a mixture of diesel components (50% for n-
dodecane, 35% for methylcyclohexane and 15% for toluene, volume
fraction) was used as the representatives of diesel for modeling diesel
combustion, while methane was used as the representatives of NG for
modeling NG combustion. Based on RCCI combustion mode, the initial
conditions and temperature boundary conditions are shown in Tables 5
and 6. The calculation models used in CFD is also listed in Table 7.
Fig. 27 shows the comparison of simulated in-cylinder HRR (heat
release rate) and pressure with experimental data with experimental
data under two models at 25% and 75% loads. Overall, both models did
well in predicting the in-cylinder pressure and HRR, the maximum error
value is 3.3%, which meets the need of precision, but the simulation
results of the mechanism with cross reactions can better fit the experi­
mental data at 25% load. From the previous analysis, it can be concluded
that cross reaction can promote the reaction rate of diesel and accelerate
the combustion. Thus, the phenomenon of higher cylinder pressure rise
rate with MODEL II at 25% load can be explained. On the contrary,
because of slower diesel combustion speed for Model I, its prediction of
in-cylinder pressure and HRR is affected. Therefore, the model with
cross-reactions (MODEL II) was chosen as the final mechanism for
modeling dual fuel engines.
6. Conclusions
In this study, employing detailed mechanisms for methane, n-
dodecane, methylcyclohexane and toluene, a reduced chemical reaction
mechanism for modeling the oxidation of natural gas-diesel dual fuel
17
Fuel 293 (2021) 120388
engines was developed using a combination of DRG, DRGEP and FSSA
mechanism simplifying methods. Extensive validations were carried out
for the reduced multi-component fuel oxidation model against experi­
mental ignition delay and flame speed data. Based on the validation
works, the effects of cross-reactions among diesel components were
analyzed under varying pressures, temperatures, and equivalence ratios,
reaction flux and sensitivity analysis were also conducted to investigate
the auto-ignition behavior under reduced multi-component mechanism
models with and without cross-reactions. Finally, the reduced mecha­
nisms were further verified by comparing with the experimental data of
engine at low and high loads. Some conclusions were drawn, as follows:
1) Validation results indicated that for each surrogate fuel, the pre­
dicted ignition delay time and flame speed of the reduced mechanism
agreed well with the detailed reaction mechanism and experimental
results over a wide range of pressure, temperature, and equivalence
ratio conditions. Also, the ignition delay times of the surrogate
blends were well predicted with the present reaction mechanisms.
2) The effects of cross-reactions on ignition are more pronounced in
medium and low temperatures. The effect of cross-reactions on the
ignition process is not sensitive to changes in the initial pressure. In
addition, the influence of cross-reactions is enhanced with an in­
crease in equivalence ratio, especially at low temperature conditions.
3) At low temperatures, when the overall reactivity level is low, adding
cross-reactions better reveals the interactions between the diesel
components, promotes the formation of diesel component in­
termediates and small active molecule, which accelerate the re­
actions of the active components and decrease the ignition delay
time. However, at higher temperatures the overall reaction speed of
the elementary elements is greatly increased, the addition of cross-
reactions does not significantly increase the reaction speeds of in­
termediate products, so the effect of cross-reactions on ignition be­
comes limited.
4) After comparing in-cylinder HRR and pressure under the multi-
component mechanism models with and without cross-reactions
with experimental data, a final reduced reaction mechanism for
dual fuel engines was determined, consisting of 150 species and 843
reactions.
CRediT authorship contribution statement
Zhenting Liu: Investigation, Writing - original draft. Liping Yang:
Conceptualization, Methodology, Supervision, Funding acquisition,
Writing - review & editing. Enzhe Song: Resources. Jiaqi Wang: Formal
analysis. Ali Zare: Writing - review & editing. Timothy A. Bodisco:
Writing - review & editing. Richard J. Brown: Writing - review &
editing.
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.
Acknowledgments
This work was supported by the Key Projects of the Natural Science
Foundation of Heilongjiang Province of China (ZD2019E003) and the
National Natural Science Foundation of China (51306041).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.120388.
Z. Liu et al. Fuel 293 (2021) 120388

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