Fuel 281 (2020) 118742

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Ignition characteristics of ethanol–hydrogen mixtures with different T

hydrogen contents at elevated initial temperatures
⁎
Yijun Henga,b, Gesheng Lia,b, Junjie Lianga,b, , Zunhua Zhanga,b
a
Key Laboratory of High Performance Ship Technology (Wuhan University of Technology), Ministry of Education, Wuhan, Hubei 430063, PR China
b
School of Energy and Power Engineering, Wuhan University of Technology, Wuhan, Hubei 430063, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Through a shock tube facility, ignition processes of ethanol–hydrogen mixtures with different hydrogen contents
Ethanol–hydrogen mixtures at elevated initial temperatures were explored experimentally and numerically. Relationships between ignition
Ignition delay time delay time and initial temperature as well as hydrogen content were analyzed. Ignition characteristics of the
Shock tube mixtures were paid attention to from the point of chemical kinetics. The result shows that at hydrogen contents
Chemical kinetics
of 0%, 70% and 90%, linear relationships are observed between logarithmic ignition delay times of the mixtures
and reciprocals of initial temperatures. At higher initial temperatures, the ignition delay time of the mixtures
does not vary monotonously with the hydrogen content. At initial temperature of 1200 K, for the mixtures with
hydrogen contents of 10% and 70%, the ignition depends on H and OH, but at hydrogen content of 90%, the
ignition is affected exclusively by H. At 1700 K, as the hydrogen content rises from 10% to 70%, effect of
reactions involving H on the ignition enhances, but when elevating continually the hydrogen content to 90%,
this kind of effect weakens. During ignition processes of the mixtures at 1200 K, ethanol is consumed mainly
through reacting with radicals, and the conversion of hydrogen occurs mainly near the ignition time points.
While at 1700 K, the time period during which the decomposition reaction dominates the ethanol consumption
extends gradually with the increasing hydrogen content, and the consumption of hydrogen also occurs over a
wider time period relative to the entire ignition period.

1. Introduction is to establish an in-cylinder combustion model via coupling chemical

To relieve energy crisis and environmental pollution, alternative
fuels for engines have been attracting increasing attention in recent
years. Ethanol is one of promising alternative fuels [1], and although it
has a broad prospect, high latent heat of vaporization, difficulty in ig-
nition at low temperatures and weak diffusivity of ethanol are not
conducive to its application to engines [2–4]. To overcome these
shortcomings of ethanol in energy conversion process, one of solutions
is to introduce a certain amount of hydrogen into ethanol engines.
Compared with ethanol, hydrogen has some advantages such as faster
flame propagation speed, lower ignition energy and stronger diffusivity
[5–7], and it can be generated from catalytic reforming of hydrous
ethanol [8]. At present, it has been demonstrated that adding hydrogen
into ethanol engines can improve in-cylinder combustion processes and
emissions [9,10].
To predict accurately in-cylinder combustion processes and pollu-
tant emissions of ethanol engines with hydrogen addition, one method
kinetic mechanisms of fuels with fluid dynamics [11,12]. To establish
this coupling model, the premise is to develop a comprehensive che-
mical kinetic mechanism for ethanol–hydrogen mixtures. As known, the
data of ignition delay time is of importance to validate and improve
chemical kinetic mechanisms. Considering the existence of high-tem-
perature (≥1100 K) combustion processes inside ethanol engines with
hydrogen addition, it is necessary to gain a deep understanding of
characteristics for ignition processes of ethanol–hydrogen mixtures at
elevated initial temperatures.
For ethanol–hydrogen mixtures, studies on in-cylinder ignition
characteristics of ethanol–hydrogen fueled engines, which are influ-
enced by both in-cylinder fluid dynamics and chemical kinetics, were
conducted [13–16]. For the spontaneous ignition processes of etha-
nol–hydrogen mixtures that are controlled by chemical kinetics, studies
were performed mainly on ethanol, hydrogen and their mixtures with
other species [17–26]. Natarajan et al. [17], Noorani et al. [18], Singh
et al. [19] and Curran et al. [20] studied the ignition characteristics of

⁎
Corresponding author at: School of Energy and Power Engineering, Wuhan University of Technology, No. 1178 Heping Avenue, Wuchang District, Wuhan, Hubei
430063, PR China.
E-mail address: liangjunwh@whut.edu.cn (J. Liang).

https://doi.org/10.1016/j.fuel.2020.118742
Received 6 March 2020; Received in revised form 26 May 2020; Accepted 15 July 2020
Available online 24 July 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
Y. Heng, et al.
Fig. 1. Schematic of the experimental facility.
ethanol and its mixtures with n-heptane. Natarajan et al. [17] and
Noorani et al. [18] used the experimental data of ignition delay time of
ethanol to fit the empirical relationship of ignition delay time under
different initial conditions. Singh et al. [19] found that the existence of
ethanol will suppress the reactivity of n-heptane/ethanol/air mixtures.
Ignition characteristics of hydrogen and its mixtures with other species
including steam [21], methane [22,23], ethane [24], propane [25]and
n-butane [26] were investigated experimentally and numerically.
Among these studies, Zhang et al. [22] found that effect of hydrogen
addition on ignition process of methane/hydrogen mixture has a de-
pendence on initial temperature. In their later study [23], it was found
that when hydrogen content does not exceed 40%, the methane
chemistry dominates the ignition process of methane/hydrogen mix-
ture. At hydrogen content of 60%, ignition of the mixture is controlled
by the combined chemistry of methane and hydrogen. While at hy-
drogen content higher than 80%, the hydrogen chemistry plays the
most important role. The study of Pan et al. [24] shows that introducing
ethane into hydrogen will impose an effect on its ignition process, and
this kind of effect is nonlinear. From the study of Tang et al. [25] it is
seen that an Arrhenius relationship exists between the ignition delay
time of propane/hydrogen mixture and the initial temperature when
the hydrogen content is lower than 70%, and such Arrhenius relation-
ship will disappear as the hydrogen content exceeds 95%. Jiang et al.
[26] found that the hydrogen addition will promote nonlinearly the
ignition of n-butane, and at hydrogen content lower than 95%, an Ar-
rhenius-type dependence of ignition delay time on initial temperature is
observed. In addition, for the n-butane–hydrogen mixtures with hy-
drogen contents of 98% and 100%, non-monotonic influence of initial
pressure on ignition delay time is found. Within the published litera-
ture, insight into spontaneous ignition characteristics of ethanol–hy-
drogen mixtures is not relatively sufficient. Due to the strong non-
linearity of chemical reaction process, it is a bit difficult to derive the
ignition characteristics of ethanol–hydrogen mixtures through simple
linear combination of those of ethanol and hydrogen.
For chemical kinetic mechanisms required for simulation of ignition
processes of ethanol and hydrogen, different schemes were developed.
Given that hydrogen is one of intermediate species in the ethanol oxi-
dation process, the reaction mechanism of hydrogen is an indispensable
part of that of ethanol. For the oxidation of ethanol, several chemical
kinetic schemes that can be used to predict it were developed. The
reaction mechanism for ethanol by Li et al. [27] consists of 39 species
and 238 elementary reactions, which was developed in a hierarchical
way based on the reaction mechanism for ethanol by Marinov et al.
[28]. The Li mechanism starts with the H2/CO sub-mechanism, fol-
lowed by C1 and C2 sub-mechanisms, and it has been validated against
the experimental data from flames and variable pressure flow reactor.
The NUI 2016 reaction mechanism by Zhang et al. [29] was developed
on the basis of the AramcoMech 2.0 mechanism [30]. Specifically, the
C0-C4 sub-mechanism of the NUI 2016 mechanism was taken from the
AramcoMech 2.0 mechanism. The NUI 2016 mechanism includes 1268
2
Fuel 281 (2020) 118742
species and 5336 elementary reactions, and originally it was proposed
to describe the n-heptane oxidation process. The PCFC mechanism for
C0-C4 species by Hemken et al. [31] involves 387 species and 2174
elementary reactions, and its H2/CO and C1-C4 sub-mechanisms were
taken from the work by Kéromnès et al. [32] and Metcalfe et al. [33],
respectively. The PCFC mechanism has been verified against the ex-
perimental data from various facilities including flow reactor coupled
with molecular-beam mass spectrometry, rapid compression machine
and shock tube coupled with laser absorption techniques. Also on the
basis of the AramcoMech 2.0 mechanism [30], the CRECK mechanism
was proposed by Bagheri et al. [34] to describe combustion processes of
C0-C3 hydrocarbons and oxygenated fuels, and this mechanism is
composed of 114 species and 1999 elementary reactions. Based on the
relationship between hydrogen and ethanol mechanisms, ignition pro-
cess of ethanol–hydrogen mixture can be simulated with the chemical
kinetic mechanism of ethanol. However, the practical applicability of
the ethanol mechanism to accurate prediction of ignition process of
ethanol–hydrogen mixture needs to be further checked.
Therefore, in the present study, spontaneous ignition experiments of
ethanol–hydrogen mixtures at different hydrogen contents are con-
ducted through a shock tube facility at elevated initial temperatures.
Modeling of constant-volume adiabatic ignition processes of the mix-
tures at the same initial conditions are also performed. Applicability of
the chemical kinetic mechanisms of ethanol to prediction of ignition
processes of ethanol–hydrogen mixtures is validated in terms of the
experimental values of ignition delay times. Then relationships between
the ignition delay time of ethanol–hydrogen mixtures and the hydrogen
content are analyzed. Additional attention is paid to the understanding
of ignition processes of ethanol–hydrogen mixtures from the perspec-
tive of chemical kinetics including analysis of sensitivity and fuel con-
sumption process.
2. Experimental method
The schematic of the shock tube facility used in the present study is
illustrated in Fig. 1. More detailed information about this experimental
facility can be found in Ref. [35], and only a brief introduction about
the facility is presented here. The lengths of high-pressure driver and
low-pressure driven sections of the shock tube are 3 and 7 m, respec-
tively, and the inner diameter of the tube is 111.3 mm. The low-pres-
sure section is covered by a heating system to maintain the temperature
inside the tube at a desired value. Four piezoelectric pressure sensors
are mounted at the side wall of the low-pressure section to record the
pressure profiles in the tube, from which the shock wave velocities can
be obtained. Based on shock wave velocities and initial conditions of
the reactant before the incident shock wave, the state parameters such
as the temperature and pressure of the reactant behind the reflected
shock wave can be figured out through the Gaseq software [36].
Moreover, a piezoelectric pressure sensor and an optical window are
mounted at the side wall adjacent to the end of the tube, which are
Y. Heng, et al. Fuel 281 (2020) 118742

employed to measure the pressure profile and the emission spectrum,

respectively, during the ignition process occurring behind the reflected
shock wave.
At the start of experiment, according to the respective partial
pressures of ethanol, hydrogen, oxygen and argon derived from the
initial conditions, they were injected into the mixing tank in turn, and
to ensure homogeneity of the mixture, the mixing tank was settled for at
least 12 h. In addition, in order to avoid condensation of ethanol, the
mixing tank was heated to a temperature of 353.15 K through a heating
system mounted outside the tank. After finishing preparation of the
reactant, a pump was used to vacuum the high- and low-pressure sec-
tions, and then the reactant in the mixing tank and the mixture of he-
lium and nitrogen, which were selected as the driver gases, were in-
jected into the low- and high-pressure sections of shock tube,
respectively. When the diaphragm broke, a shock wave formed, and
then the reactant behind the reflected shock wave ignited sponta-
neously.
As indicated in Introduction, the present study mainly focuses on
Fig. 2. Typical signals of pressure and OH* chemiluminescence for ignition of
ignition characteristics of ethanol–hydrogen mixtures at various hy-
ethanol–hydrogen–oxygen–argon mixture at 10.128 atm, 1337 K and equiva-
drogen contents with high initial temperatures, and thus in the present lence ratio of 1.0. The hydrogen content and the dilution ratio are 10% and
study, initial conditions including pressure, temperature and equiva- 95%, respectively. IDT indicates the ignition delay time.
lence ratio were set at fixed values, and only the hydrogen content was
altered. The specific experimental conditions and the corresponding
3. Numerical method
compositions of reactants in the present study are listed in Table 1. The
calculation method of mole fractions of components of the reactants can
In the present study, zero-dimensional constant-volume adiabatic
be referred to our previous study [35]. From the point of comprehen-
ignition processes of ethanol–hydrogen mixtures under the initial con-
sively validating and improving chemical kinetic mechanisms of fuels,
ditions mentioned above were simulated with the CHEMKIN-PRO
it is also necessary to determine the experimental values of ignition
software, and modeled values of ignition delay times were determined
delay times under such conditions selected. In addition, with respect to
according to variation of OH mole fraction with the time [38,39]. Ac-
the hydrogen contents presented in Table 1, they were selected based
cording to the studies by Zhang et al. [23] and Hong et al. [40], when
on nonlinear variations of ignition delay times of ethanol–hydrogen
the initial temperature is high enough (the corresponding ignition delay
mixtures with the increasing hydrogen content at different initial
time is lower than about 1.5 ms), non-ideal effects in shock tube such as
temperatures, as indicated in the subsequent section Results and dis-
boundary layer effect are weak, and thus the ignition behind the re-
cussion. Specifically, changes in ignition delay times of ethanol–hy-
flected shock wave can be assumed to be a constant-volume process
drogen mixtures at high hydrogen contents are relatively more sig-
without considering the pressure rise. In the present study, most of
nificant than those at low hydrogen contents, and thus values of
values of ignition delay times for ethanol–hydrogen mixtures are lower
hydrogen contents given in Table 1 were selected.
than 1.5 ms, and thus the above assumption was employed to derive the
Based on the above experimental facility and procedures, profiles of
modeled ignition delay times for the mixtures.
pressure and OH* emission for ignition of ethanol–hydrogen mixtures
As suggested in Introduction, the practical applicability of the
can be obtained, and a typical result is exhibited in Fig. 2. In this study,
ethanol mechanism to prediction of ignition process of ethanol–hy-
the pressure signal is used to determine the start time point of ignition
drogen mixture needs further verification. In the present study, ignition
period. When the slope of the OH* emission signal reaches its max-
processes of ethanol, hydrogen and their mixtures were modeled with
imum, the intersection point of the corresponding tangent line of OH*
the chemical kinetic mechanisms mentioned above. Subsequently the
emission signal and the baseline defines the end time point of ignition
modeled values of ignition delay times were compared to the corre-
period.
sponding experimental values obtained through the above shock tube
Uncertainties of experimental values of temperature and pressure
facility, and the result is shown in the next section.
for the reactant behind the reflected shock wave mainly originate from
non-ideality of the gas and measurement error of shock wave velocity
[37]. According to the theories about one-dimensional normal shock 4. Results and discussion
wave and error analysis, for the present experiments, the measurement
error of shock wave velocity is about 0.17%, which leads to the tem- 4.1. Ignition delay times of ethanol–hydrogen mixtures
perature uncertainty of 0.36% and the pressure uncertainty of 0.62%
for reactant behind the reflected shock wave. Shown in Fig. 3 are experimental values of ignition delay times of
ethanol–hydrogen mixtures with hydrogen contents of 0%, 70%, 90%
and 100% at given equivalence ratio, pressure and temperatures as well

Table 1
Experimental conditions and compositions of the reactants.
Temperature (K) Pressure (atm) Equivalence ratio Hydrogen content (%) Compositions of the reactants (%)

Hydrogen Ethanol Oxygen Argon

1100–1600 10 1 0 0 1.25 3.75 95

70 1.556 0.67 2.778 95
90 2.571 0.286 2.143 95
100 33.33 0 1.667 95

3
Y. Heng, et al.
Fig. 3. Comparisons between experimental and modeled values of ignition
delay times for ethanol–hydrogen mixtures. Symbols denote the experimental
data, and lines means the modeled data.
as the corresponding modeled values derived based on NUI 2016, Li,
PCFC and CRECK mechanisms. In addition, experimental values of ig-
nition delay times of the mixtures at hydrogen contents of 10%, 50%
and 85% were also obtained, and Table S1 in the Supplementary ma-
terial presents the specific experimental values of ignition delay times
of the mixtures at related hydrogen contents.
As presented in Fig. 3, at the given initial conditions, the ignition
delay time of ethanol–hydrogen mixtures reduces as the temperature
increases. Through comparing the modeled values of ignition delay
times of the mixtures from different chemical kinetic mechanisms with
the corresponding experimental values, it is found that further im-
provement and optimization are necessary for some of mechanisms in
accurate prediction of ignition delay times of the mixtures under certain
initial conditions. Specifically, for pure ethanol, the modeled ignition
delay times from NUI 2016, Li, PCFC and CRECK mechanisms agree
well with the experimental values. But after introducing a certain
amount of hydrogen into ethanol, the NUI 2016, PCFC and CRECK
mechanisms exhibit better capability than the Li mechanism in pre-
dicting ignition processes of ethanol–hydrogen mixtures. As for pure
hydrogen, at the studied initial conditions, the modeled values from Li
mechanism are closer to the experimental ones. But with the increasing
initial temperature, the modeled ignition delay times of pure hydrogen
from these four mechanisms tend to be consistent. Then as a result, it
can be concluded reasonably that further improvement is necessary for
the Li mechanism to accurately predict ignition processes of etha-
nol–hydrogen mixtures when the hydrogen content is not 0% or 100%.
Relatively speaking, for pure hydrogen, the NUI 2016, PCFC and
CRECK mechanisms predict accurately the trend of ignition delay time
with the initial temperature. Considering the objective of the present
study is to reveal ignition characteristics of ethanol–hydrogen mixtures,
only one reaction mechanism is employed to conduct the following
study. Here the NUI 2016 mechanism is selected for the following
analysis.
From Fig. 3 it can also be found that at hydrogen contents of 0%,
70% and 90%, the ignition delay time of ethanol–hydrogen mixtures
Table 2
Summary of related parameters in Eq. (1).
Hydrogen content (％) Empirical correlation
0 τ1 = 1.31 × 10−4exp(19033/T)
70 τ2 = 1.70 × 10−5exp(21521/T)
90 τ3 = 1.26 × 10−5exp(21153/T)
Fuel 281 (2020) 118742
exhibits an Arrhenius relationship with the initial temperature, which
means that the logarithmic ignition delay time rises linearly with the
increase of reciprocal of initial temperature [25]. But when the hy-
drogen content reaches 100%, the Arrhenius relationship no longer
exists. In order to clearly and quantitatively describe the Arrhenius
relationship between the ignition delay time and the initial temperature
for the mixtures at hydrogen contents of 0%, 70% and 90%, Eq. (1) [19]
is employed in the present study:
E
τ = C·exp ⎛ a ⎞
⎝ RT ⎠ (1)
where τ is the ignition delay time (μs), C a constant, Ea the total
activation energy (kcal·mol−1), R the universal gas constant
(1.986 × 10−3 kcal·mol−1·K−1) and T the initial temperature (K). The
relevant parameters in Eq. (1) for ethanol–hydrogen mixtures at hy-
drogen contents of 0%, 70% and 90% are presented in Table 2. In ad-
dition, for mixtures with hydrogen contents of 10%, 50% and 85%, the
Arrhenius relationships are also fitted based on Eq. (1), and the result is
given in Table S2 of the Supplementary material. It should be pointed
out that it is based on experimental values of ignition delay times at the
studied initial conditions that the parameters presented in Tables 2 and
S2 are derived.
As shown in Table 2, at hydrogen contents of 0%, 70% and 90%, the
correlation coefficients of fitting between ignition delay times of etha-
nol–hydrogen mixtures and initial temperatures are 0.997, 0.991 and
0.990, respectively, indicating good fitting achieved [41]. The pure
ethanol (i.e., the hydrogen content is equal to 0%) has the lowest total
activation energy of 37.80 kcal·mol−1, which is close to the value ob-
tained by Barrza-Botet et al. [41]. This value is lower than those for
ethanol–hydrogen mixtures with hydrogen contents of 70% and 90%,
suggesting that the ignition delay time of pure ethanol depends on the
temperature over the studied temperature range more weakly than that
of the mixtures. That is to say that as the initial temperature alters, the
change occurring in the ignition delay time for pure ethanol is relatively
smaller than that for the mixtures at hydrogen contents of 70% and
90%. Thus it can be deduced reasonably that there exists a critical
temperature, and when the initial temperature is lower than this critical
temperature, the ignition delay time of pure ethanol is shorter than that
of ethanol–hydrogen mixtures. When the initial temperature is higher
than the critical temperature, the opposite result will be observed. This
phenomenon can be found in Fig. 3, in which the orange solid circles
represent the critical temperatures.
In Fig. 3, it is also seen that the ignition delay time of ethanol–hy-
drogen mixtures continually shortens with the increasing hydrogen
content within the relatively low temperature range. But as the tem-
perature increases, the reduction rate of ignition delay time of pure
hydrogen gradually decreases. When the temperature rises to a certain
value, the curve of the ignition delay time with the initial temperature
for pure hydrogen intersects with that for ethanol–hydrogen mixtures,
which indicates that the ignition delay time of ethanol–hydrogen mix-
tures no longer reduces monotonously with the increasing hydrogen
content at this initial temperature. To more clearly illustrate the effect
of hydrogen content on the ignition delay time of ethanol–hydrogen
mixtures, changes of ignition delay times with the hydrogen content at
different initial temperatures were derived through the NUI 2016 me-
chanism, and the result is shown in Fig. 4. Besides, the corresponding
fitted values of ignition delay times obtained from Eq. (1) are also
Ea (kcal·mol−1) R-Square Temperature range for fitting (K)
37.80 ± 0.99 0.997 1213–1553
42.74 ± 1.99 0.991 1208–1474
42.01 ± 1.55 0.990 1105–1368
4
Y. Heng, et al.
Fig. 4. Detailed variations of modeled and fitted ignition delay times of etha-
nol–hydrogen mixtures with the increasing hydrogen content at different initial
temperatures. Lines represent modeled values of ignition delay times derived
from the NUI 2016 mechanism, and symbols denote the fitted values of ignition
delay times obtained from Eq. (1).
presented in Fig. 4.
From Fig. 4 it is demonstrated that variations of ignition delay times
of ethanol–hydrogen mixtures with the increasing hydrogen content
depend on the initial temperature. Specifically, at temperatures of
1100, 1200 and 1300 K, as the hydrogen content increases, the ignition
delay time of the mixtures first remains unchanged or changes rela-
tively slowly, and then significant changes occur in the ignition delay
time when the hydrogen content increases to a certain value, which is
strongly related to the initial temperature. At initial temperature of
1100 K, the hydrogen content at which remarkable changes happening
in the ignition delay time for ethanol–hydrogen mixtures is about 90%,
while at 1300 K, the corresponding hydrogen content is about 80%.
When the initial temperature continually increases, it is seen that no
sharp but continuous decline occurs in the ignition delay time of the
mixtures with the increasing hydrogen content. And the higher the
initial temperature is, the more linearly the ignition delay time reduces
within the low hydrogen content range. At high initial temperatures,
when the hydrogen content exceeds a certain value, the ignition delay
time of the mixtures starts to increase, as shown in Fig. 4, and this is
consistent with the phenomenon presented in Fig. 3 that at high initial
temperatures, the cure of variation of ignition delay time with the
temperature for hydrogen intersects with that for ethanol–hydrogen
mixtures with the hydrogen content not equal to 0%. Meanwhile, as the
initial temperature increases, it is observed that a decrease exists in the
hydrogen content at which the ignition delay time starts to increase.
In addition, through comparing the modeled values of ignition delay
times for ethanol–hydrogen mixtures at different temperatures with the
corresponding fitted results obtained from Eq. (1), it can be found that
at the studied initial temperatures of 1200 to 1600 K, the deviations in
ignition delay time between modeled and fitted values are relatively
marginal, which proves the accuracy of the fitting equation within this
initial temperature range. However, at initial temperatures of 1100 and
1700 K, the modeled values of ignition delay times differ relatively
significantly from the fitted ones, thus indicating the limit of the fitting
equation. This is mainly because the total activation energy of etha-
nol–hydrogen mixtures varies with the range of initial temperature,
which is similar to that of methane–hydrogen mixtures [42]. The ac-
tivation energies in equations given in Tables 2 and S2 were derived
mainly based on the experimental ignition delay times within the initial
temperature range of 1200–1600 K. While at initial temperatures of
1100 and 1700 K, the activation energy of the mixtures changes, which
is not taken into consideration in equations presented in Tables 2 and
5
Fuel 281 (2020) 118742
Fig. 5. Sensitivity coefficients of elementary reactions influencing significantly
ignition delay time of ethanol–hydrogen mixtures with various hydrogen con-
tents at initial temperatures of 1200 and 1700 K.
S2. Thus deviations between the modeled and fitted values of ignition
delay times for the mixtures at 1100 and 1700 K are observed. To
clearly shows the deviations between modeled and fitted values of ig-
nition delay times of ethanol–hydrogen mixtures at studied initial
conditions, the specific modeled and fitted values are provided in Table
S3 of the Supplementary material.
In order to gain some insight into the chemical kinetic character-
istics of changes observed in the ignition delay time of ethanol–hy-
drogen mixtures under different temperatures and hydrogen contents,
the sensitivity of ignition delay time [23] to the elementary reactions
was analyzed based on the NUI 2016 mechanism, and the result is
shown in Fig. 5. From the perspective of H atom, it is seen that the
reaction between H and O2 to form O and OH (i.e., R5) has the strongest
influence on the ignition of ethanol–hydrogen mixtures regardless of
the initial temperatures and hydrogen contents. In Fig. 5(a), at initial
temperature of 1200 K and hydrogen contents of 10% and 70%, it is
observed that the ignition of ethanol–hydrogen mixtures significantly
depends on H and OH when comprehensively considering these reac-
tions. However, when the hydrogen content rises to 95%, obvious in-
creases occur in the absolute values of sensitivity coefficients of ele-
mentary reactions associated with H such as R5, R3, R2, R406 and R28,
while the absolute values of sensitivity coefficients of reactions related
to other radicals such as R99 and R408 reduce. This phenomenon in-
dicates that the dependence of ignition of ethanol–hydrogen mixtures
on H atom enhances under this high hydrogen content, and this kind of
dependence on H seems to be exclusive.
In Fig. 5(b), at initial temperature of 1700 K, when the hydrogen
content increases from 10% to 70%, the absolute values of sensitivity
coefficients for reactions associated with H including R5, R3, R406,
R28, and R335 increase, which means that effect of reactions involving
H on the ignition of ethanol–hydrogen mixtures is elevated. However,
when the hydrogen content continually increases to 90%, the absolute
values of sensitivity coefficients of these reactions decline. That is to say
that the influence of H atom on the ignition of ethanol–hydrogen
mixtures with hydrogen content of 90% at the temperature of 1700 K
Y. Heng, et al. Fuel 281 (2020) 118742

Fig. 6. Variations of mole fractions of ethanol and hydrogen with the time at different hydrogen contents during the time interval from zero to the ignition time point.
Symbols denote the corresponding ignition time points under various hydrogen contents.

weakens, which differs from that at initial temperature of 1200 K.

4.2. Analyses of consumption processes of ethanol–hydrogen mixtures

To further understand ignition characteristics of ethanol–hydrogen

mixtures, according to the modeled ignition processes of ethanol–hy-
drogen mixtures, mole fractions of ethanol and hydrogen versus the
time under different temperatures and hydrogen contents were ana-
lyzed, and the result is presented in Fig. 6. The initial temperatures are
1200 and 1700 K, and the hydrogen content is from 10% to 90% with
the interval of 10%.
In Fig. 6(a), at the initial temperature of 1200 K, mole fractions of
ethanol and hydrogen remain almost unchanged at the initial stage of
ignition. As for ethanol consumption in ignition processes, although the
ethanol content varies with the hydrogen content, the time points
corresponding to complete consumption of ethanol under different
hydrogen contents are basically adjacent to each other. Only in the case
of high hydrogen content and low ethanol content (90% hydrogen
content), the time point for complete consumption of ethanol deviates
significantly from others. For hydrogen in ignition processes, at all
hydrogen contents studied, the hydrogen is mainly consumed rapidly
near the ignition time points. Moreover, when the studied hydrogen
content is between 10% and 70%, with the decrease of the hydrogen
content, the complete consumption of hydrogen will occur in advance.
However, within the hydrogen content range of 70% to 90% studied, as
the hydrogen content decreases, the time point for complete con-
sumption of hydrogen is delayed. In addition, from the point of view of
the time of duration for consumption, the consumption of ethanol lasts
for a longer time than hydrogen, and the complete consumption of
ethanol happens before hydrogen.
While when the initial temperature is raised from 1200 to 1700 K,
compare Fig. 6(b) with (a), and it can be found that the initial ignition
period during which mole fractions of ethanol and hydrogen remain
Fig. 7. Rates of production of hydrogen via related elementary reactions in
nearly unchanged has almost disappeared, which means ethanol and ignition processes of ethanol–hydrogen mixtures with various initial tempera-
hydrogen start to react from the beginning of ignition process. In ad- tures and hydrogen contents.
dition, when the hydrogen content is 80% or less, there also exists a
generation process for hydrogen before its consumption. But the time of
consumes the largest amount of hydrogen. In Fig. 7(a), at initial tem-
duration for hydrogen consumption relative to the entire ignition
perature of 1200 K, these elementary reactions mainly occur near ig-
period significantly extends under the studied hydrogen contents. Ad-
nition time points and last for relatively short times, thus leading to the
ditionally, when hydrogen and ethanol coexist, over the entire hy-
fast decrease of mole fraction of hydrogen near ignition time points, as
drogen content range studied, the time when hydrogen is consumed on
shown in Fig. 6(a). In Fig. 7(b), when the initial temperature rises from
a large scale is gradually delayed with the increase of hydrogen content.
1200 to 1700 K, it can be seen that durations of these elementary re-
Based on Fig. 6, to further figure out the dominant reaction channels
actions extend significantly relative to the corresponding ignition delay
for fuel molecules, rates of production of hydrogen and ethanol through
times, which is the root of changes of hydrogen mole fractions over
related elementary reactions in ignition processes of ethanol–hydrogen
wider time periods shown in Fig. 6(b). Besides, from Fig. 7(a) and (b) it
mixtures were analyzed, and the result as well as the related initial
is observed that at different initial temperatures, peaks of rates of
conditions are presented in Figs. 7 and 8. Table 3 shows the specific
generation reactions for hydrogen decrease continually with the in-
details of reactions in Figs. 7 and 8.
crease of the hydrogen content. This is mainly attributed to the fact that
For hydrogen, as shown in Fig. 7(a) and (b), its consumption is
in ignition processes of ethanol–hydrogen mixtures, hydrogen is
mainly related to OH and O, and the reaction of hydrogen with OH

6
Y. Heng, et al.
Fig. 8. Variations of rates of production of ethanol through related elementary reactions with the time in ignition processes of ethanol–hydrogen mixtures at different
temperatures and hydrogen contents.
generated mainly through reactions of H with the species containing
carbon, which means the hydrogen generation is related to the ethanol
content when considering the species containing carbon only originates
from ethanol. Thus if the hydrogen content rises, the ethanol content
will then decrease, consequently resulting in the decrease in the amount
of hydrogen generated.
As for ethanol, comparing Fig. 8(a) with (b), a difference is observed
in reaction types of ethanol consumption during ignition processes of
ethanol–hydrogen mixtures. At initial temperature of 1200 K, reactions
between ethanol and radicals dominate the consumption of ethanol
over the whole ignition processes. Additionally, with the increase of
hydrogen content, durations of consumption reactions for ethanol
shorten gradually, thus leading to changes in mole fraction of ethanol
with the time shown in Fig. 6(a). When the initial temperature increases
7
Fuel 281 (2020) 118742
to 1700 K, the decomposition reaction R394 plays the leading role for
the ethanol consumption at initial stages of ignition periods. With the
increasing hydrogen content, peaks of rates of consumption reactions
for ethanol decrease continually, but the time period during which the
decomposition reaction R394 dominates the ethanol consumption ex-
tends. In other words, when more ethanol is mixed with hydrogen,
effect of reactions between ethanol and radicals on consumption of
ethanol enhances. Thus it can be deduced, to some extent, that the more
ethanol there exists, the more radicals there will generate. In addition,
when the time proceeds, the importance of reactions of ethanol with
radicals rises and the dominant position of these reactions is achieved
gradually for ethanol consumption. Besides, from the point of view of
time periods during which ethanol- and hydrogen-related reactions
occur, reactions between ethanol and radicals happen ahead of
Y. Heng, et al.
Table 3
Main elementary reactions related to generation and consumption of hydrogen
and ethanol in ignition processes of ethanol–hydrogen mixtures.
Species Number Elementary reactions
hydrogen R3 H2 + OH < = > H + H2O
R2 H2 + O < = > H + OH
R155 CH2O + H < = > HCO + H2
R44 CH4 + H < = > CH3 + H2
R28 HO2 + H < = > H2 + O2
ethanol R407 C2H5OH + OH < = > SC2H4OH + H2O
R406 C2H5OH + H < = > SC2H4OH + H2
R414 C2H5OH + H < = > PC2H4OH + H2
R415 C2H5OH + OH < = > PC2H4OH + H2O
R394 C2H5OH < = > C2H4 + H2O
R417 C2H5OH + CH3 < = > PC2H4OH + CH4
R408 C2H5OH + HO2 < = > SC2H4OH + H2O2
reactions of hydrogen with radicals, thus indicating that ethanol is
more competitive for radicals than hydrogen.
5. Conclusion
In the present study, ignition delay times of ethanol–hydrogen
mixtures at initial pressure of 10 atm and equivalence ratio of 1.0 with
elevated initial temperatures were measured through a shock tube fa-
cility. The hydrogen content ranges from 0% to 100%. Several chemical
kinetic mechanisms used to predict ignition processes of the mixtures
was validated against the experimental data in terms of the CHEMKIN-
PRO software. Then relationships between the ignition delay time and
the initial temperature as well as the hydrogen content were analyzed.
Chemical kinetic analyses of ignition characteristics of the mixtures
were performed from different points. Main conclusions of the present
study are as follows:
(1) At hydrogen contents of 0%, 70% and 90%, the logarithmic ignition
delay time of ethanol–hydrogen mixtures varies linearly with the
reciprocal of initial temperature, indicating an Arrhenius relation-
ship occurs. But for pure hydrogen, this kind of relationship no
longer exists.
(2) With the increasing hydrogen content, nonlinear changes are ob-
served in ignition delay times of ethanol–hydrogen mixtures at
various initial temperatures. Especially, for the mixtures under
higher initial temperatures, the ignition delay time will not alter
monotonously with the hydrogen content.
(3) At initial temperature of 1200 K, for ethanol–hydrogen mixtures
with hydrogen contents of 10% and 70%, the ignition depends on H
and OH, but at hydrogen content of 90%, the ignition is affected
exclusively by H. At initial temperature of 1700 K, as the hydrogen
content rises from 10% to 70%, the effect of reactions involving H
on the ignition enhances, but when elevating continually the hy-
drogen content to 90%, this kind of effect weakens.
(4) At initial temperature of 1200 K, ethanol is consumed mainly
through reacting with radicals, and the conversion of hydrogen into
other species occurs mainly near the ignition time points. While at
initial temperature of 1700 K, the time period during which the
decomposition reaction is dominant for the ethanol consumption
extends gradually with the increasing hydrogen content. In addi-
tion, ethanol is more competitive for radicals than hydrogen.
CRediT authorship contribution statement
Yijun Heng: Conceptualization, Methodology, Investigation,
Writing-original draft. Gesheng Li: Validation, Formal analysis. Junjie
Liang: Resources, Writing-review & editing, Supervision, Data curation.
Zunhua Zhang: Writing-review & editing.
8
Fuel 281 (2020) 118742
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work is financially supported by the National Natural Science
Foundation of China (grant numbers 51779199 and 51809204) and the
Fundamental Research Funds for the Central Universities (WUT:
2019IVB027 and 2019IVA087).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118742.
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