Fuel 288 (2021) 119669

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Fuel
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Full Length Article

Effects of equivalence ratio and blending ratio on the ignition delays of

n-pentane/hydrogen mixtures under engine relevant pressure
Xue Jiang *, Rui Zhang , Fuquan Deng
State Key Laboratory of Multiphase Flows in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China

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

Keywords: In this work, new ignition delay times of n-pentane/hydrogen binary mixtures were measured at a pressure of 20
Hydrogen atm, equivalence ratios of 0.5, 1.0, and 2.0 using a shock tube. Literature Pentane Isomer model is found to well
N-Pentane capture the ignition delay times of n-pentane/hydrogen mixtures under the current condition. Kinetic analyses
Ignition delay
are performed to interpret the equivalence ratio dependence for n-pentane/hydrogen blends and to understand
Equivalence ratio
the interplay chemistry between the two fuels. It is found that the ignition delay times of all the n-pentane/
Fuel blending
hydrogen mixtures in this study show the equivalence ratio dependence similar to pure n-pentane. The reaction
pathway indicates that n-pentane reacts independently from the hydrogen after blending. Hydrogen addition
only gives the moderate promotion on n-pentane ignition for small hydrogen proportions since the H radicals in
the dual-fuel system were mostly supplied to the n-pentane H-abstractions and the oxidation chemistry hydrogen
is inhibited after blending.

1. Introduction
The current concern on oil consumption and environmental prob­
lems have promoted the use of new energy sources. Hydrogen presents
as a promising energy carrier, but challenges remain in the usage of pure
hydrogen in IC engines, gas turbines, and boilers [1–3]. Specifically,
hydrogen has strong diffusibility, wide flammable range, fast flame
speed, and high chemical activity, the above-mentioned properties have
led to the concern of combustion control and safety [1–4]. Despite the
challenges, hydrogen is still an attractive alternative fuel because it is
completely carbon free [2]. A sustainable compromise is to blend the
hydrogen with hydrocarbons [5], which does offer the potential to
adjust the combustion properties of both hydrogen and hydrocarbon
fuels, realize the lean burn technology in the combustion appliance, and
reduce the carbon footprint.
The combustion of hydrogen-enriched methane (natural gas) has
been most widely studied from both aspects of the application and
fundamental. Indeed, the blending of hydrogen into methane or natural
gas contributed to the expansion of operating load limits and the
enhancement of thermal efficiency for IC engines [6–9]. Besides, dual-
fuel gas turbine operation of hydrogen/natural gas demonstrated that
lower carbon and NOx emissions can be achieved simultaneously by
using hydrogen-enriched blends to implementing lean-burning [10–12].
To better guide the dual-fuel application, the laminar flame speeds of
hydrogen/methane or hydrogen/natural gas have been measured using
a variety of apparatus, such as the combustion bomb [13–16], stagna­
tion plane flame [17–19], and heat flux [20]. In addition, the ignition
delay times of hydrogen and methane combined fuel have been
comprehensively studied via shock tubes [21–23] and rapid compres­
sion machines [24,25]. The above-mentioned studies show that
hydrogen addition can intensify the methane laminar flame by
increasing the H radical concentration in the reaction zone and preheat
zone. Similarly, the ignition delay time of methane can be reduced by
hydrogen addition under different temperatures due to the accelerated
accumulation of free radicals.
The use of hydrogen-doped blends was identified as an interim to­
wards the long-term transformation of the “hydrogen economy” [12].
On this account, a growing body of research has been conducted to
better understand the combustion property of hydrogen-enriched larger
molecular transportation fuels. Some studies report on the combustion
and emission characteristics of hydrogen-enriched alcohol fuels
[26–29], gasoline [30–33], diesel [34–36], etc. in engine applications.
The ignition delay time is the important fundamental data for the design
of combustion devices such as engines and gas turbines, furthermore, it
is the benchmark data for the validation of chemical kinetic models.
However, fundamental understanding of the ignition delay

* Corresponding author.
E-mail address: xuejiang1128@xjtu.edu.cn (X. Jiang).

https://doi.org/10.1016/j.fuel.2020.119669
Received 10 October 2020; Received in revised form 29 October 2020; Accepted 1 November 2020
Available online 15 November 2020
0016-2361/© 2020 Elsevier Ltd. All rights reserved.
X. Jiang et al. Fuel 288 (2021) 119669

characteristics of hydrogen blended larger hydrocarbons is far from 2. Experimental and numerical approaches
comprehensive, only a few researchers have studied the ignition delays
of hydrogen blending with DME [37,38], ethane [39,40], propane 2.1. Shock tube device
[41,42], and butane [43–45].
n-Pentane is an n-paraffin composed of five carbon atoms that exist The present measurements are conducted in a stainless steel shock
within practical fuels [46] and petroleum feed-stocks [47]. It is tube of 11.5 cm internal diameter. The specifications of this shock tube
considered as the representative component of surrogates or primary are described in detail in Ref. [23]. In simple terms, as shown in Fig. 1,
reference fuels (PRFs) [48,49], for which several studies took n-pentane the shock tube has a 2 m high pressure driver section and a 7.3 m low
directly as the simulated gasoline [50,51]. Being in the transition posi­ pressure driven section divided by double polyethylene terephthalate
tion between gaseous and liquid alkanes [52], the reaction pathway of n- (PET) diaphragms. Four PCB 113B26 pressure sensors are installed
pentane can be analogous to larger hydrocarbons to offer substantial along the end of the driven section at equal spacing. Fluke PM 6690 time
insights into the oxidation kinetics [53]. For these reasons, the ignition counters are used to measure the time interval between the shock wave
delay times of n-pentane have been measured using rapid compression reaching each pressure sensor to determine the shock wave velocity.
machines by Westbrook et al. [54], Ribaucour et al. [55], Piehl et al. The pressure and CH* emission signal at the shock tube endwall are
[53], and Bugler et al. [56], it is found that n-pentane gives the two-stage recorded by the Hamamatsu CR 131 photomultiplier and PCB 113B03
ignition property under low to intermediate temperatures, the first stage pressure sensor, respectively. The ignition delay is defined as the time
ignition is closely related to the alkylperoxy isomerization. Shock tube from the arrival of the incident shock wave (t = 0) until the extrapola­
studies focusing on the high temperature ignition delays of n-pentane tion of the maximum slope of CH* emission trace to the baseline, as
were also reported by different research groups [52,56–58] from at­ shown in Fig. 2. The typical attenuation rates of the incident shock of
mospheric pressure to 530 atm, and equivalence ratios from 0.3 to 2.0. this shock tube is dP/dt = 4.2%/ms [23]. The experimental uncertainty
In order to guide the application of hydrogen-enriched combustion, of the measured ignition delay time is ±20% assessed according to the
it is necessary to study the ignition delays of n-pentane/ hydrogen references [23].
mixtures. Chemical interaction between binary fuel derivatives may
happen under engine-relevant conditions and act on the combustion
2.2. Preparation of test mixture
properties. Mehl and co-workers [59] found that in the kinetic model of
multiple gasoline surrogate components, it is necessary to consider the
Test mixtures are prepared based on the Dalton partial pressure law
inter-reaction between alkyl and alkyl-peroxy to capture the combustion
characteristics. However, the influence of hydrogen blending on the
ignition delays of n-pentane at various equivalence ratios is not clear.
Therefore, the first objective of this study is to conduct ignition delay
measurements of n-pentane/hydrogen blends from lean to rich condi­
tions (equivalence ratio of 0.5 to 2.0) and at engine-relevant high
pressure (20 atm) using a shock tube. The measured ignition delay data
are used to validate the capability of the available kinetic model and
identify any crucial reactions for the dual-fuel ignition chemistry. The
second objective is to investigate the equivalence ratio dependence
characteristics for n-pentane/hydrogen blends at different degrees of
hydrogen doping. Finally, the effect of hydrogen blending on the high
temperature ignition behavior of n-pentane will be compared with that
of methane to see whether hydrogen blending has any generalized effect
on large and small n-alkanes.

Fig. 2. Definition of ignition delay time.

Fig. 1. Diagram of the experimental configuration.

2
X. Jiang et al. Fuel 288 (2021) 119669

in a stainless steel tank of 128 L in volume and sit for more than 12 h.
The “air” in this paper is a mixture of oxygen and argon in the molar
ratio of 21:79. The ignition delay times of the argon-diluted (fixed
dilution ratio of 80%) n-pentane/hydrogen/ “air” blends were measured
at the equivalence ratios of 0.5, 1.0, and 2.0. The test mixture conditions
are shown in Table1. The purities of the reactants in this study are higher
than 99.999%.
indicating that the Pentane Isomer Model is able to capture the high
temperature ignition delay time of hydrogen from low to high pressures,
and lean to rich conditions.
Note that the Pentane Isomer Model can also well capture the igni­
tion delay times of pure n-pentane and n-pentane/hydrogen binary
mixtures in this study, as shown in Fig. 3. Therefore, this model was used
in this study to calculate the ignition delays of hydrogen, n-pentane, and
their binary mixture, as well as to conduct relevant kinetic analyses.

2.3. Kinetic simulations and model validation 3. Results and discussion

The simulations of the ignition delay time in the shock tube were 3.1. Effect of equivalence ratio
performed using the 0-D constant volume and adiabatic solver in the
Chemkin Pro software [60]. The non-ideal pressure rise ratio (dP/dt = Fig. 3 (a)–(e) gives both the experimental measurements and nu­
4.2%/ms) of the shock tube is considered in numerical modelling using merical simulations for the equivalence ratio dependence of the ignition
the SENKIN/VTIM method [61]. delay time for various n-pentane/hydrogen mixtures at 20 atm.
The Pentane Isomers Model developed by Bugler et al. [56,62,63] in In Fig. 3 (a), the auto-ignition delays for pure n-pentane at the
the NUI Galway is used for the simulation in this study. This model equivalence ratios of 0.5, 1.0, and 2.0 were compared, wherein the
consists of 697 species and 3216 reactions. Both the chemical kinetics highest reactivity was observed for the fuel-lean mixture, followed by
and thermodynamics of n-pentane, iso-pentane and neo-pentane in this the fuel-stoichiometric mixture, and the fuel-rich mixture gives the
model are well developed [63] and been validated by both the macro­ lowest reactivity. Such an equivalence ratio dependence characteristic is
scopic ignition delay data of the pentane isomers in shock tube and rapid consistent with the previous observation by Bugler et al. [56] for the
compression machine [56], as well as the microscopic JSR data [62]. ignition behavior of n-pentane/air mixtures, as well as the high tem­
Therefore, one of the objectives of this study is to evaluate the chemical perature ignition of most alkanes [68]. It is found that the chain-
kinetics for the oxidation of n-pentane/hydrogen binary mixtures of this branching reaction H + O2 ⇔ O + OH is always the most sensitive
model through experiments. promoting reactions during the high temperature ignition of n-alkanes
A proper kinetic model of dual-fuel ignition must first be able to [56,68], the rate of which is relevant to the concentration of the H
accurately predict the ignition behavior of single components. The radical and oxygen. On the one hand, the oxygen concentration in the
hydrogen chemical kinetics play a significant role and been considered reaction system reduces with the increase of the equivalence ratio. On
as the prerequisite and foundation in the model development for all the other hand, RH + H ⇔ R + H2 is the main oxidation path of n-
hydrocarbon fuels since the oxidation of which involving the combus­ pentane at high temperatures [56], the increase of equivalence ratio
tion chemistry and some crucial elementary reactions of H, O, OH, HO2, lead to more effective competition for H atom via RH + H ⇔ R + H2 and
etc [64]. As it is important, extensively studies of hydrogen ignition the less pronounced chain-branching of H + O2 ⇔ O + OH. As a result,
delay properties have been reported in the literature. The Pentane Iso­ the ignition delay time of the n-pentane becomes even longer with the
mer Model was developed based on the widely recognized hydrogen increasing equivalence ratio.
base-mechanism proposed by the NUI Galway, the performance of this Also, note that in Fig. 3 (a), a convergence of both the measured and
hydrogen sub-model has previously been validated against the ignition simulated ignition delays for n-pentane of each equivalence ratios occurs
delay time pure hydrogen and hydrogen-containing mixtures in the at about 1150 K and 20 atm indicating that the effect of equivalence
references [23,44,65–67]. Moreover, Hu et al. [65] recently did ratio becomes lessens as the temperature decreases in the current con­
comprehensive measurements on the ignition delay times of argon ditions. This phenomenon is due to the gradually important role of fuel
diluted hydrogen using a shock tube from low to high pressure (1.2 to radicals in the oxidation of n-pentane at intermediate to low tempera­
16 atm) and lean to rich conditions (equivalence ratios of 0.5–2.0) with tures, wherein the reaction RH + HO2 ⇔ R + H2O2 provides the
the similar test mixture composition as that in this study. They consid­ consequent chain-branching sequence [56].
ered the influence of residual H-atom to guarantees the reliability of the As shown in Fig. 3 (e), the simulated ignition delay times of pure
data and evaluated the predictive performance of hydrogen ignition for hydrogen are identical at high temperatures above 1190 K indicating the
many literature models. The Pentane Isomer Model was validated approximate reactivity at different equivalent ratios, this trend is
against the hydrogen ignition delay of Hu et al. [65], the measurements consistent with previous literature experiments [41,69] (The predictions
and simulations show good agreement (see the supporting material) of the Pentane Isomer Model and the above literature data also show
good agreements, gives in the supporting materials). For the high tem­
Table 1 perature ignition of hydrogen, besides H + O2 ⇔ O + OH, the hydrogen-
Composition of fuel mixture. relevant reactions O + H2 ⇔ H + OH and OH + H2 ⇔ H + H2O are also
Mixtures ϕ XC5H12 XH2 (%) XO2 (%) XAr (%) the important chain reaction channels [68]. The increase of the equiv­
(%) alence ratio will inevitably decrease the oxygen concentration and
P100 (100% C5H12) 0.5 0.259 0 4.144 95.597 restrain the reaction H + O2 ⇔ O + OH, however, the following chain
1.0 0.512 0 4.096 95.392 sequence of O + H2 ⇔ H + OH and OH + H2 ⇔ H + H2O become more
2.0 0.998 0 3.992 95.010 frequent with the increase of hydrogen concentration. As a result, the
P30H70 (30% C5H12 70% 0.5 0.221 0.515 4.046 95.218
H 2) 1.0 0.426 0.993 3.902 94.679
hydrogen ignition delays yield weak equivalence ratio dependence at
2.0 0.795 1.855 3.644 93.706 high temperatures.
P10H90 (10% C5H12 90% 0.5 0.155 1.395 3.875 94.575 However, as the temperature decreases, the fuel-rich hydrogen
H 2) 1.0 0.288 2.589 3.596 93.527 mixtures ignite slightly faster than the fuel-stoichiometric and the fuel-
2.0 0.503 4.527 3.144 91.826
lean mixtures give the longest ignition delay times. With the decrease of
P5H95 (5% C5H12 95% H2) 0.5 0.107 2.036 3.750 94.107
1.0 0.194 3.677 3.387 92.742 temperature, H + O2 ⇔ O + OH is not that favored because it is an
2.0 0.324 6.162 2.838 90.676 endothermic reaction with high activation energy [70]. Meanwhile, its
H100 (100% H2) 0.5 0 3.471 3.471 93.058 competing chain-termination reaction H + O2 + M ⇔ HO2 + M con­
1.0 0 5.915 2.957 91.128 sumes much of the H and O2 [22], therefore, the higher oxygen con­
2.0 0 9.13 2.282 88.588
centration in the fuel-lean mixture has a slight decelerating effect on the

3
X. Jiang et al. Fuel 288 (2021) 119669

Fig. 3. Ignition delay times and simulations of n-pentane/hydrogen mixture at various equivalence ratios and pressure of 20 atm.

ignition at the moment.

It is interesting to notice that the ignition delay times of all the n-
pentane/hydrogen mixtures in this study show the equivalence ratio
dependence similar to n-pentane indicating the n-pentane chemistry
gives the obvious effect on the ignition chemistry after fuel blending, as
shown in Fig. 3 (b)–(d). This point of view is further supported by the
following sensitivity analysis. The brute force sensitivity analysis for the
P5H95 mixtures is performed at 1300 K, 20 atm, and various equiva­
lence ratios in Fig. 4 to identify the most sensitive reactions affecting the
ignition delay of the binary fuels. The sensitivity coefficient is defined as
S = log (τ (2ki)/τ (0.5ki))/log(2/0.5), where τ is the ignition delay time,
ki is the rate coefficient of specific reactions. Note that the H-atom ab­
stractions of n-pentane compete for H radicals and lead to the inhibited
chain-branching through H + O2 ⇔ O + OH thus increase the ignition
delay time, while the decomposition of n-pentane is the sensitive igni­
tion promoting reaction in the current condition. With only 5% n- Fig. 4. Sensitivity analysis of the P5H95 mixtures at 1300 K, 20 atm, and
pentane blending, some reactions relevant to the carbon-based com­ various equivalence ratios.
pounds show the high sensitivity coefficients, those reactions compete
for free radicals with the oxidation reactions of hydrogen, leading to the 3.2. Effect of hydrogen on n-pentane reactivity
n-pentane-like ignition behavior and equivalence ratio dependence for
the n-pentane/hydrogen mixtures. In Fig. 5, the ignition delay times of n-pentane blended with
hydrogen are compared under different equivalence ratios. It is seen that
under each equivalence ratio, the ignition delay times always decrease

4
X. Jiang et al.
Fig. 5. Ignition delay times of n-pentane/hydrogen blends under various
hydrogen blending ratios (a) ϕ = 0.5 (b) ϕ = 1.0 (c) ϕ = 2.0.
with the increasing hydrogen ratio due to the higher reactivity and
shorter ignition delay times of hydrogen relative to n-pentane. The
similar effects of hydrogen blending on the ignition delays of other n-
alkanes are reported in the previous studies [22,23,41–43] illustrate that
for a general binary n-alkane/hydrogen system, the increase of hydrogen
blending can always promote the reactivity and lead to shorter ignition
delay times. In addition, the influence of hydrogen blending under
different equivalence ratios are similar, indicating the change of
equivalence ratio does not alter the impact of fuel blending under the
current conditions.
To interpret the influence of hydrogen blending on the reactivity of
n-pentane, reaction pathway analysis is performed at 1300 K, 20 atm,
and ϕ = 1.0. It is observed in Fig. 6 that under the current conditions, the
oxidation of pure n-pentane mainly proceeds through the uni-molecular
decomposition and the H-atom abstraction. Most of the n-pentane
5
Fuel 288 (2021) 119669
decomposed to produce NC3H7 (17.7%) followed by β- scission to yield
C3H6 and C2H4, a small amount (1.7%) of the fuel also generates PC4H9
and CH3 via the decomposition pathway. Indeed, the vast majority of n-
pentane consumed via H-atom abstraction to produce C5H11-1(22.6%),
C5H11-2 (38.8%), and C5H11-3 (17.1%), respectively. Those fuel radicals
then mostly proceed via the following β-scission reactions. Such an
observation for the high temperature reaction pathway has previously
been confirmed by the experimental and theoretical studies of n-pentane
[56,63]. Note that the reaction pathway indicates that n-pentane reacts
independently from the hydrogen after blending, following almost the
same pathway as that for the pure n-pentane. In other words, there is no
inter-reaction between n-pentane/fuel radicals and hydrogen in the
current conditions. It is found that the addition of hydrogen slightly
accelerates the H-atom abstractions of n-pentane, especially promotes
that by the H radicals due to the presence of the higher H radical con­
centration after hydrogen blending. In a previous work, Man et al. [42]
examined the ignition delay properties of propane/hydrogen mixtures
and conclude that hydrogen addition results in the promoted reaction
pathways via C3H8 + H ⇔ H2 + nC3H7, and C3H8 + H ⇔ H2 + iC3H7
during the oxidation. In another related work [23], it is observed that
adding hydrogen into methane can accelerate the production and con­
sumption of H radical during the oxidization thus contribute to the total
reaction rate. Hence, in agreement with previous studies, we conclude
that the high temperature reactivity of alkane can be promoted by the
introduced H radical from hydrogen after blending.
3.3. Effects of hydrogen blending on the auto-ignition of methane and n-
pentane
Methane is the representative of small alkane, while n-pentane rep­
resents for large alkane, the effects of hydrogen addition on ignition
delay of large and small alkanes are compared in this study. Fig. 7 gives
the computed effect of hydrogen mole fraction on the ignition delays for
the stoichiometric methane and n-pentane at 20 atm, 1300 K. It is seen
from Fig. 7 that the ignition delay time of methane reduces by about
67% with 20% hydrogen addition, while reduces by about 89% when
further increase the hydrogen fraction to 40%. This tendency is consis­
tent with previous experiments in the literature [23] indicating a small
amount of hydrogen addition can effectively promote the ignition delay
of methane. However, for n-penatne, the ignition delay is reduced by less
than 7% with 40% hydrogen blending, obvious reduction in ignition
delay is observed only with higher hydrogen ratios. Such an effect of
hydrogen addition to n-pentane was also found much alike to that for
propane and butane in the literature [41,42,44], indicating the influence
of hydrogen on the high temperature ignition of C3–C5 n-alkanes are
similar.
To understand the reactivity of methane and n-pentane blended with
hydrogen, the normalized H radical rate of consumption for pure
hydrogen, 20% hydrogen/80%methane, 20%hydrogen/80%n-pentane,
60% hydrogen/40%methane, and 60% hydrogen/40% n-pentane mix­
tures are analyzed. As shown in Fig. 8 (a), the H radicals are mainly
consumed via the competing pathways of H + O2 ⇔ O + OH (R1) and H
+ O2 (+M) ⇔ HO2 (+M) (R9), H + O2 (+AR) ⇔ HO2 (+AR) (R10) during
the ignition of pure hydrogen. (R1) is well known as the key chain-
branching step of the radical chain process for the high temperature
oxidation of both hydrogen and alkanes, while the three-body reactions
(R9) and (R10) are the chain-termination steps of hydrogen ignition
[22].
For the high temperature oxidation of pure methane, the initial
generation of the radical pool is governed by CH4 + O2 ⇔ CH3 + HO2
[70]. Because the above-mentioned reaction for methane is slower
relative to the rates of the similar type reactions or decomposition re­
action for larger alkanes, the ignition delay time of methane is longer in
comparison to higher-order alkanes [71]. Note that after hydrogen
addition, shown in Fig. 8 (b), (R129) account for more than 40% of the
total H radical rate of consumption at the initial stage of ignition
X. Jiang et al.
Fig. 6. Reaction pathway of n-pentane at 1300 K, 20 atm, ϕ = 1.0 (Black: P100 mixture, Red: P30H70 mixture, Green: P5H95 mixture). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 7. Simulated effect of hydrogen blending on the auto-ignition of stoi­
chiometric methane and n-pentane using Pentane Isomer Model at 20 atm,
1300 K.
indicates that the auto-ignition of methane is promoted by hydrogen.
That is to say, once hydrogen is added to methane, the fast-reacting
hydrogen produces H radical to promote the initial consumption of
methane via CH4 + H ⇔ CH3 + H2 thus contribute to the development of
the radical pool. Also note that for the ignition of 20%hydrogen/80%
methane mixture, the reaction system is influenced by the hydrogen
chemistry since most of the H radicals are still consumed by the reaction
channels of hydrogen oxidation via (R1), (R9), and (R10).
For the 20%hydrogen/80%n-pentane mixture, shown in Fig. 8 (c),
the H radical consumption is governed by the H-atom abstraction re­
actions of n-pentane which show higher consumption rates relative to
that via (R1), (R9), and (R10) during the early inducing time, that is to
say, the n-pentane chemistry plays a dominant role in the dual-fuel re­
action system. This is reasonable because it is easier to cross the lower
activation barrier than the higher one when chemical reactions occur.
The lower activation barriers of the H-atom abstractions of n-pentane
(R2312), (R2313), and (R2314) allow the relevant chain-branching to
happen more quickly than that from the reaction (R1), therefore (R1) is
less competitive for the H radicals relative to the n-pentane H-atom
abstractions in the dual-fuel system. When further increase the hydrogen
ratio to 60%, as shown in Fig. 8 (d) and (e), the normalized H radical rate
6
Fuel 288 (2021) 119669
of consumption shows similar properties to the 20% hydrogen ratio
cases, indicating the similar dominant reactions in consuming the H
radicals.
In general, the reasons why 20% hydrogen blending can obviously
promote the ignition of methane but has an unremarkable effect on the
ignition of n-pentane are as follows: (1) Hydrogen addition provides the
alternative path via CH4 + H ⇔ CH3 + H2 besides the initial radical
production reaction of pure methane (CH4 + O2 ⇔ CH3 + HO2) thus
promotes methane oxidation. In addition, hydrogen itself ignites much
faster than methane, besides, most of the H radicals in the dual-fuel
system are consumed along the oxidation pathway of hydrogen, so the
reactivity is improved greatly after fuel blending. (2) Although hydrogen
ignites much faster than n-pentane, the ignition of the n-pentane/
hydrogen mixture is dominated by n-pentane chemistry. That is, the H
radical consumption rate via hydrogen oxidation path reduces signifi­
cantly due to the radical competition, and the H radicals in the system
are mostly supplied to the n-pentane H-abstractions, the above reasons
result in a less significant ignition promotion effect of hydrogen
addition.
4. Conclusions
The ignition delay time of pure n-pentane and n-pentane/hydrogen
blends were measured using a shock tube under engine relevant pres­
sure. The predictions of the Pentane Isomer Model developed by NUI
Galway show good agreement with the n-pentane/hydrogen ignition
delay data. It is interesting to notice that the ignition delay times of all
the n-pentane/hydrogen mixtures in this study show the equivalence
ratio dependence similar to pure n-pentane indicating the ignition de­
lays of the binary mixtures are dominated by n-pentane chemistry after
blending. The reaction pathway indicates that n-pentane reacts inde­
pendently from the hydrogen after blending. Simulation and kinetic
analysis indicate that 20% Hydrogen addition only gives the moderate
promotion on n-pentane ignition since the H radicals in the dual-fuel
system were mostly supplied to the n-pentane H-abstractions and the
oxidation chemistry hydrogen is inhibited after blending. Methane
ignition delay can be obviously accelerated by 20% hydrogen addition,
it is found that the competitive effect of methane on H radical is weak
and hydrogen addition can promote methane oxidation by activating the
X. Jiang et al.
Fig. 8. Normalized H radical rate of consumption (normalized through the total rate of consumption for H radical) at 1300 K, 20 atm, and ϕ = 1.0 (Dash-dot line:
moment of ignition).
initial radical production via CH4 + H ⇔ CH3 + H2.
CRediT authorship contribution statement
Xue Jiang: Conceptualization, Methodology, Investigation, Writing
- original draft, Visualization, Writing - review & editing, Funding
acquisition. Rui Zhang: Investigation, Visualization. Fuquan Deng:
Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This study was supported by the National Natural Science Founda­
tion of China (Grant number: 51876164), China Postdoctoral Science
Foundation Grant (Grant number: 2018M640987 and 2019T120907),
State Key Laboratory of Engines, Tianjin University (K2019-05), and
Jiangsu Province Key Laboratory of Aerospace Power System, China
(CEPE2020009).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2020.119669.
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