i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0

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Emission characteristics and heat release rate

surrogates for ammonia premixed laminar flames

Mengzhen Cheng a, Haiou Wang a,*, Hua Xiao b, Kun Luo a, Jianren Fan a
a
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, PR China
b
Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of
Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, PR China

highlights

Laminar ammonia flames are simulated in atmospheric and high-pressure conditions.

Four mechanisms of ammonia combustion are considered.

The pollutant emission achieves a minimum around an equivalence ratio of 1.1~1.5.

Heat release rate surrogates are proposed to estimate the heat release rate distribution.

article info abstract

Article history: Ammonia is a carbon-free fuel that has the potential to meet increasing energy demand
Received 6 April 2020 and to reduce CO2 emissions. In the present work, the characteristics of pollutant emis-
Received in revised form sions in ammonia premixed laminar flames are investigated using one-dimensional sim-
18 November 2020 ulations, and heat release rate (HRR) surrogates for ammonia combustion are proposed.
Accepted 22 January 2021 Both atmospheric and high-pressure conditions were considered, and four representative
Available online 25 February 2021 mechanisms for ammonia combustion were employed. It is shown that the total emission
of NO and NH3 achieves a minimum around an equivalence ratio (f) of 1.1 under atmo-
Keywords: spheric conditions, and there is no noticeable emission of NO and NH3 for f ¼ 1.1 ~ 1.5
Ammonia combustion under high-pressure conditions. Three HRR surrogates, [NH3][OH], [NH2][O], and [NH2][H],
Premixed laminar flames were proposed based on the analysis of HRR and elementary reaction profiles. The per-
Pollutant emission formance of HRR surrogates was found to vary with equivalence ratios. For example, with
Heat release rate surrogate the Miller mechanism, [NH3][OH], [NH2][O], and [NH2][H] have the best performance under
atmospheric conditions at f ¼ 1.15, 0.95 and 1.05, respectively, and under high-pressure
conditions at f ¼ 1.11, 0.87 and 0.96, respectively. Similar conclusions can also be drawn
with other mechanisms. These findings provide valuable insights into emission control
and flame identification of ammonia combustion.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: wanghaiou@zju.edu.cn (H. Wang).
https://doi.org/10.1016/j.ijhydene.2021.01.154
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
13462 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0
Introduction
In order to reduce the emissions of CO2 while meeting the
growing demand for energy, alternative for fossil fuels should
be explored. Both hydrogen and ammonia are carbon-free
fuels and they are attractive energy carriers [1,2]. According
to its physical properties, hydrogen is difficult to be com-
pressed and liquefied so that its storage and transport are
major challenging problems [3]. Ammonia consists of 17.8%
hydrogen by mass and it can be easily liquefied by com-
pressing to 9.9 atm at atmospheric temperature or cooling to
33.4  C at atmospheric pressure. Because of these advan-
tages, ammonia has been regarded as a potential fuel for
environmental considerations to address global warming is-
sues. In fact, ammonia has been used as a fuel in laboratories
[4]. However, there are several challenges for ammonia com-
bustion applications, such as low premixed flame velocity,
low flammability and high NOx emission [5,6]. There have
been some attempts made to develop practical combustion
devices using ammonia but their performance was not satis-
factory [7,8]. Insightful studies of ammonia combustion are
required to gain better understanding of ammonia combus-
tion and emission behaviors, and to enable improved design
of industrial engines.
Recent studies on ammonia combustion focus on laminar
flames, which are helpful to reveal the fundamental com-
bustion characteristics of ammonia, to develop and verify
ammonia combustion mechanisms, and to provide a refer-
ence for the study of ammonia turbulent combustion.
Ammonia laminar flames have been studied by both exper-
iments and numerical simulations. Experimental data exist
for model development and validation [9e12]. For example,
Duynslaegher et al. [9] experimentally investigated the flame
structure of eight premixed NH3/H2/O2 flames at low pres-
sure and measured profiles of temperature as well as mole
fractions of important species. The experimental data were
used by the same authors to validate an improved ammonia
combustion mechanism [13]. Appropriate combustion
mechanism is the prerequisite for reliable simulations. A
short review of the chemical mechanisms for ammonia
combustion is provided here. Miller et al. [14] developed the
first complete mechanism for ammonia combustion which
was validated against the experimental data for NH3/O2 and
NH3/H2/O2 flames. Lindstedt et al. [15] improved the Miller
mechanism [14] and explored the NO formation character-
istics. In order to obtain better predictions, Duynslaegher
et al. [13] modified four elementary reactions in the Konnov
mechanism [16], and proposed a reduced mechanism in their
simulations of engine problems. Mathieu et al. [17] measured
ignition delay time of NH3/O2/Ar flames at high pressure and
proposed a new mechanism from the mechanism of Dagaut
et al. [18] with improved predictions of ammonia ignition
delay time. Combustion of ammonia blended with hydro-
carbon fuel was also studied [19e21]. For exemple, Tian et al.
[19] developed a mechanism for methane and ammonia
combustion, and modeled various NH3/CH4/O2 premixed
flames at low pressure. The Tian mechanism was further
improved by Okafor et al. [22] for modeling ammonia-based
flames.
Heat release rate (HRR) is an important quantity in com-
bustion characterization. The spatial distribution of HRR
provides an important basis for determining where the flame
locates in reacting flows. The most direct measurement of
turbulent burning rate would be an evaluation of local heat
release rates [23]. Unfortunately, direct measurement of HRR
is impossible as its calculation involves accurate measure-
ments of temperature and all species concentrations simul-
taneously. Alternatively, HRR profiles could be estimated with
information of certain species concentrations. For example,
Mulla et al. [24] compared the product of H and CH2O con-
centrations ([H][CH2O]) and [OH][CH2O], and suggested that
both surrogates provide close estimates of HRR in laminar
methane/air premixed flames. Najm et al. [25] concluded that
HCO mole fraction was a suitable indicator of HRR of methane
flames in two-dimensional unsteady vortical flows based on
numerical and experimental studies. Wang et al. [23] exam-
ined the validity of existing HRR surrogates in turbulent
methane/air premixed flames and proposed a new HRR
surrogate with improved performance. Despite of the above-
mentioned works, there is no relevant study on HRR surro-
gates for ammonia combustion, which motivates the present
work.
Most previous studies of ammonia combustions were
conducted under low or atmospheric conditions. For example,
the pollutant emission characteristics of ammonia combus-
tion under atmospheric conditions were examined by Hay-
akawa et al. [26]. However, industrial combustors such as gas
turbines mostly operate under high temperature and pressure
conditions. It is of interest to explore the ammonia combus-
tion behaviors such as pollutant emissions in more practical
conditions.
In this context, the objectives of the present work are to
compare the characteristics of pollutant emissions in
ammonia combustion under atmospheric and high pressure
conditions, and to propose proper HRR surrogates for these
flames. The paper is organized as follows. Section Numerical
methods describes the setup of different cases and the details
about the numerical tools, and shows the verification of the
four mechanisms used in this work. The results of ammonia
combustion are shown and discussed in Section Results and
discussion. Finally, conclusions are drawn in section
Conclusions.
Numerical methods
In the present work, NH3/air premixed laminar flames under
atmospheric (1 atm) and high pressure (20 atm) are simulated.
For the atmospheric pressure cases, the reactant temperature
is 298 K, while that for the high-pressure cases is 800 K. A
range of equivalence ratios are considered in both the atmo-
spheric and high-pressure cases. A freely-propagating flame
configuration is considered. The simulations were performed
using Cantera [27], an open-source suite of tools for combus-
tion problems involving chemical kinetics, thermodynamics,
and transport processes. A mixture-averaged transport model
is used. Note that only laminar ammonia flames are consid-
ered in this work. Turbulent ammonia flames will be explored
in our future work.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0 13463

The governing equations of continuity, radial momentum,

energy and species are solved in a cylindrical coordinate,
which are shown as follows [28]:

ru
þ 2rV ¼ 0 (1)
vz


vV v vV
ru þ rV2 ¼ L þ m (2)
vz vz vz

 X
vT v vT vT X
rcp u ¼ l  jk cp  hk Wk u_ k (3)
vz vz vz k
vz k

Fig. 1 e Flame speed calculation of NH3/air flame at 0.1 MPa

vYk vjk
ru ¼  þ Wk u_ k (4) and 298 K compared with experimental data from
vz vz
Hayakawa et al. [30] (
), Takizawa et al. [31] (-), Pfahl et al.
where r is the density, u is the axial velocity, V is the scaled [32] (þ) and Ronney et al. [33] (:).
radial velocity, L is the pressure eigenvalue, m is the dynamic
viscosity, cp is the heat capacity at constant pressure, T is the
temperature, l is the thermal conductivity, Yk is the species
To overcome the low burning velocities of pure ammonia
mass fraction, jk is the species diffusive mass flux, hk is the
flames, combustions of a blend of ammonia and other gas,
species enthalpy, Wk is the species molecular weight, and u_ k is
such as H2, CO and CH4, have been studied [34,35]. The
the species molar production rate.
mechanisms are further assessed in Fig. 2, which shows the
As mentioned in Sec. Introduction, there are a few
premixed flame speeds of NH3/H2 flames under atmospheric
ammonia mechanisms available in the literature [13e19,22].
conditions [36]. As can be seen, the Miller and Lindstedt
Four representative chemical mechanisms for ammonia
mechanisms provide more accurate results in lean regions.
combustion are employed in the present work, i.e. the Miller
In contrast, the Mathieu mechanism is good at predicting
mechanism [14,29], the Lindstedt mechanism [15], the
premixed flame speed in a wide range of equivalence ratio.
Mathieu mechanism [17], and the Okafor mechanism [22].
The Okafor mechanism under-predicts the premixed flame
These mechanisms are described and assessed by comparing
the numerical and experimental results in the following.
The Miller mechanism [14] represents the first complete
mechanism for ammonia combustion and an improved
version with 20 species and 73 reactions [29] is utilized in the
present work. The Lindstedt mechanism [15] accounts for 22
species and 95 reactions including those contributing to the
formation and consumption of NOx. The Mathieu mecha-
nism [17] is based on the Dagaut mechanism [18] and it
consists of 55 species and 275 reactions. It is proposed to
predict ignition delay time for ammonia combustion over a
wide range of operating conditions. The Okafor mechanism
[22] is a detailed reaction mechanism developed based on
GRI Mech 3.0 and the Tian mechanism [19], which provides
improved laminar premixed flame velocity and NO concen-
tration predictions.
Laminar premixed flame speed is an essential parameter
for premixed flames, which could be computed both numer-
ically and experimentally. Fig. 1 shows the unstrained pre-
mixed flame speed of NH3/air flames calculated with the four
mechanisms at a pressure of 0.1 MPa and a temperature of
298 K. The experimental results from Refs. [30e33] are also
presented. It is seen that the premixed flame speed increases
firstly with increasing equivalence ratio and then decreases.
The maximum premixed flame velocity is achieved at around
f ¼ 1.1. All four mechanisms predict the correct trend as
compared to the experiments. The predictions of the Mathieu
and Okafor mechanisms are particularly good. Both the Miller
and Lindstedt mechanisms over-predict the flame speeds.
Discrepancy of the experimental results between various Fig. 2 e Flame speeds calculation of 40% (top), 50% (middle)
research groups also exist due to uncertainties in the mea- and 61.5% (bottom) NH3 in NH3/H2 mixture flames under
surements [30e33]. atmospheric conditions.
13464 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0
speeds compared to the experimental data. It can also be
concluded that the incorporation of hydrogen can promote
the propagation of ammonia-based flames.
Next, validations of the mechanisms at elevated pressure
are performed. Shrestha et al. [37] reported flame speeds under
high pressure conditions with different levels of hydrogen
addition based on experimental measurements. The compar-
ison of flame speeds for NH3/H2 flames [37] as a function of H2
content in the fuel blend are shown in Fig. 3. As can be seen,
the premixed flame speed increases with increasing amount of
H2 in the fuel and decreasing pressure for all mechanisms. The
Mathieu mechanism provides the best results among all
mechanisms. Although the predictions of the Miller and
Lindstedt mechanisms are promising in NH3/H2 flames under
atmospheric conditions, they over-predict the flame speeds at
elevated pressure.
Results and discussion
In this section, the mechanisms described in the previous
section are employed for the study of ammonia flames. First,
the ammonia flame structures and emission characteristics of
NOx and NH3 are presented. Then the heat release rate sur-
rogates for Ammonia flames are proposed and their implica-
tions for turbulent ammonia flames are discussed.
Emission characteristics
Reduction of NOx emission is of great importance for indus-
trial applications. It has been well understood that using
equilibrium results for estimating NOx emissions is not suffi-
cient as the formation of NOx depends on its residence time in
the combustor. In this section, the emission characteristics of
NOx in the products of ammonia/air premixed laminar flames
Fig. 3 e Laminar flame speed of NH3/H2/air at 473 K and
varying H2 content at 4 ¼ 1.1 and pressure of 5 (a) and 7
(b) bar.
under various conditions are examined. In addition, the con-
centration of unburned fuel, NH3, in the products is also
studied as ammonia itself is also a pollutant.
Fig. 4 shows the flame structure using the Miller mecha-
nism under atmospheric and high-pressure conditions with
an equivalence ratio of f ¼ 1. The flame thickness in the high-
pressure case is significantly thinner, and its value calculated
from the temperature profiles is about 0.045 mm. In contrast,
the flame thickness in the atmospheric case is 1.259 mm,
which is much larger than its counterpart under high-
pressure conditions and is also larger than the flame thick-
ness of hydrocarbon fuels [5] under atmospheric conditions.
The flame thicknesses of ammonia combustion using
different mechanisms are provided in Table 1.
As can be seen in Fig. 4, ammonia is completely reacted in
stoichiometric flames, and the nitrogen element in ammonia
is mostly converted into N2. As for NOx in the products, NO
concentration is much greater than that of NO2 and N2O, so we
focus on NO formation in the following analysis.
The concentrations of NH3 and NO vary significantly with
equivalence ratio, and the position where they are sampled.
Here, the emission characteristics at 4 cm downstream of the
reaction zone (characterized by the location of maximum heat
release rate) at various equivalence ratios under atmospheric
conditions are plotted in Fig. 5. It is seen that under atmo-
spheric conditions, the mole fraction of NO first increases
and then decreases with increasing equivalence ratio, and
the maximum NO mole fraction is achieved around an
equivalence ratio of 0.9. This observation can be explained as
follows.
The oxidation of NHi (i ¼ 0, 1, 2) may lead to NO formation,
mainly through HNO reactions, or to NO consumption
through NHi þ NO reactions, depending on the concentration
of radical pools such as O and OH [14]. The abundance of O and
Fig. 4 e Flame structure under atmospheric (a) and high-
pressure (b) conditions using the Miller mechanism.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0 13465

Table 1 e Flame thicknesses calculated with the four

mechanisms under atmospheric and high-pressure
conditions.
Miller Lindstedt Mathieu Okafor
Atmospheric 1.259 mm 1.201 mm 2.675 mm 1.811 mm
High-pressure 0.045 mm 0.044 mm 0.083 mm 0.053 mm

OH radicals in the reaction zone at lean conditions, especially

at equivalence ratios from 0.9 to 1.0 as shown in Fig. 6, favors
Fig. 6 e Mole fractions of O, OH, and H in the reaction zone
the oxidation of NHi by O and OH through the following
under atmospheric (left) and high-pressure (right)
reactions:
conditions using the Miller mechanism.
NH þ O ¼ NO þ H ðR1Þ

NH þ OH ¼ HNO þ H ðR2Þ
NH2 þ O ¼ HNO þ H ðR3Þ
HNO þ H ¼ H þ NO ðR4Þ
N þ OH ¼ NO þ H ðR5Þ
These reactions therefore facilitate the production of NO in
the flames. In contrast, in rich regions a lacking of radicals
such as O and OH prevents formation of NO from NHi and
promotes NHi-NHi interactions through which NHi is con-
verted to N2 without producing NO. Fig. 5 also indicates that
the concentration of NH3 is negligible when f < 1.1 and it in-
creases monotonically with equivalence ratio in rich regions.
The total emission of NO and NH3 drops to a minimum
amount around f ¼ 1.1, and the same trend was observed in
Hayakawa [26]. Therefore, it is concluded that the slightly rich
condition of f ¼ 1.1 can simultaneously reduce NO and NH3.
The predictions provided by the four mechanisms show
the same trend but the Mathieu mechanism predicts lower
concentrations of NO than other mechanisms and there is less
unburned NH3 in rich regions for the Lindstedt mechanism.
Under high-pressure conditions, the peak of emission of
NO occurs at a smaller equivalence ratio of f ¼ 0.8 compared
with that under atmospheric conditions as shown in Fig. 7,
and this tendency is again related to the behaviors of O and
OH radicals (not shown). High temperature benefits oxidation
of NH3, so there is little NH3 left in burned gas until the
equivalence ratio reaches 1.5. There is almost no noticeable
emission of NO or NH3 at equivalence ratio from 1.1 to 1.5. This
result has significant implications for emission reduction in
practical engines of ammonia combustion, showing that in

Fig. 5 e Emission characteristics at 4 cm downstream of the position of maximum heat release rate at various equivalence
ratios under atmospheric conditions using the Miller mechanism (a), the Lindstedt mechanism (b), the Mathieu mechanism
(c) and the Okafor mechanism (d).
13466 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0

Fig. 7 e Emission characteristics at 4 cm downstream of the position of maximum heat release rate at various equivalence
ratios under high-pressure conditions using the Miller mechanism (a), the Lindstedt mechanism (b), the Mathieu
mechanism (c) and the Okafor mechanism (d).

high pressure conditions there is a wide range of operating
conditions where the pollutant emission could be minimized.
Heat release rate surrogates
In this section, HRR surrogates for ammonia premixed flames
are proposed and their performance is evaluated. The spatial
distributions of total HRR and heat release from elementary
reactions are first examined, and the heat release rates of
some major reactions contribute considerably to the total HRR
which are showed in Fig. 8, where the profiles of different
reactions are also compared with the total HRR profile. The
normalized profiles of following three reactions:
NH3 þ OH ¼ NH2 þ H2 O ðR6Þ
NH2 þ O ¼ HNO þ H ðR7Þ
NH2 þ H ¼ NH þ H2 ðR8Þ
show overall good agreement with that of the total HRR as
can be seen in Fig. 9, which shows the spatial distribution of
normalized reaction and total HRR at stoichiometric and at-
mospheric condition using the Miller mechanism. Based on
the above analysis, [NH3][OH], [NH2][O] and [NH2][H] are pro-
posed as HRR surrogates and their performance under various
conditions is evaluated quantitatively. The representative
profiles of HRR and [NH3][OH] are shown in Fig. 10. In order to

Fig. 8 e Spatial distribution of HRR of major reactions and Fig. 9 e Spatial distribution of normalized reaction and
total HRR at stoichiometric and atmospheric condition total HRR at stoichiometric and atmospheric condition
using the Miller mechanism. using the Miller mechanism.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0
Fig. 10 e Definition of characteristics of the spatial
distribution profiles of HRR and concentrations product.
quantify the difference between the two profiles, two non-
dimensional variables, (x  x0)/H0 and H/H0, are utilized. The
variable x0 is defined as the location of the maximum heat
release rate and H0 is the width of heat release rate profile at
its half maximum value; x and H are the corresponding vari-
ables for the [NH3][OH] profile. It is obvious that for a perfect
HRR surrogate, (x-x0)/H0 is zero and H/H0 is unity. The results
of (x  x0)/H0 and H/H0 for various HRR surrogates are pre-
sented in the following. Only results based on the Miller
mechanism are provided here. Similar trends are obtained
with other mechanisms as shown in the supplementary
material.
Fig. 11 shows H/H0 and (x-x0)/H0 as a function of equiva-
lence ratio under atmospheric conditions for various HRR
Fig. 11 e H/H0 (a) and (x-x0)/H0 (b) as a function of
equivalence ratio at atmospheric conditions using the
Miller mechanism.
13467
surrogates. It is readily observed that (x-x0)/H0 approaches
zero and H/H0 approaches unity for [NH3][OH], [NH2][O], and
[NH2][H] at f ¼ 1.15, 0.95, and 1.05, respectively, suggesting
these HRR surrogates work reasonably well at specific equiv-
alence ratios. The performance of HRR surrogates is further
verified by plotting HRR against its surrogates, which has been
used to evaluate the HRR surrogate performance [23e25].
Fig. 12 shows HRR versus HRR surrogates with f ¼ 0.95, 1.05,
and 1.15 under atmospheric conditions. The quantities are
normalized using their respective peak values. It is confirmed
that [NH3][OH], [NH2][O] and [NH2][H] show good spatial cor-
relations with HRR at these equivalence ratios.
Finally, Fig. 13 shows H/H0 and (x-x0)/H0 as a function of
equivalence ratio under high-pressure conditions for various
HRR surrogates. Again, the performance of HRR surrogates
varies for different equivalence ratios. In particular, the
equivalence ratio corresponding to the optimal performance
is 1.11, 0.87 and 0.96 for [NH3][OH], [NH2][O] and [NH2][H],
respectively. Consistent results are obtained by plotting HRR
against its surrogates at these equivalence ratios as shown in
Fig. 14.
Flame front identification is one of the most challenging
tasks for experimental studies of ammonia flames [38,39]. The
present work proposed several HRR surrogates that perform
Fig. 12 e The spatial variation of HRR compared to species
concentration product at equivalence ratio of 0.95, 1.05 and
1.15 at 1 atm and 298 K using the Miller mechanism.
13468 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0
Fig. 13 e H/H0 (a) and (x-x0)/H0 (b) as a function of
equivalence ratio at high-pressure conditions using the
Miller mechanism.
Fig. 14 e The spatial variation of HRR compared to species
concentration product at equivalence ratio of 0.87, 0.96 and
1.11 at 20 atm and 800 K using the Miller mechanism.
reasonably well under various conditions, and improved our
understanding of ammonia flame front identification. It is
worth noting that the species involved in these HRR surro-
gates could be measured based on laser diagnostics [39e42], so
that the results of the present work could be applied to
experimental studies directly. Although the proposed HRR
surrogates are based on laminar flames, they are expected to
be valid also under turbulent conditions. It has been shown
that although turbulence influences the flame structures in
physical space, the chemical pathways of the flames are
largely unchanged [43,44]. The proposed HRR surrogates of
ammonia combustion will be explored for turbulent ammonia
flames in our future work.
Conclusions
The present work focuses on the characteristics of pollutant
emission, especially the emission of NO and NH3, and the
surrogates of heat release rate (HRR) for ammonia unstrained
premixed laminar flames. Simulations conducted under at-
mospheric (P ¼ 1 atm and T ¼ 298 K) and high-pressure
(P ¼ 20 atm and T ¼ 800 K) conditions using Cantera were
performed and four representative chemical mechanisms for
ammonia combustion, i.e. the Miller mechanism, the Lind-
stedt mechanism, the Mathieu mechanism and the Okafor
mechanism, were employed.
Under atmospheric conditions, the mole fraction of NO at
4 cm downstream of the maximum heat release rate location
first increases and then decreases with increasing equiva-
lence ratio, and the maximum NO mole fraction is achieved
around f ¼ 0.9. The mole fraction of NH3 increases with
increasing equivalence ratio when f > 1.1. The total emission
of NO and NH3 achieves a minimum around f ¼ 1.1. Under
high-pressure conditions, the peak of NO emission occurs at a
smaller equivalence ratio compared to that under atmo-
spheric conditions. There is no noticeable emission of NO or
NH3 for f ¼ 1.1 ~ 1.5 for high-pressure flames.
Three HRR surrogates were proposed by analyzing the
profiles of HRR and elementary reactions, i.e. [NH3][OH],
[NH2][O] and [NH2][H]. Two non-dimensional variables,
(x  x0)/H0 and H/H0, are employed to evaluate the HRR sur-
rogate performance quantitatively. The performance of the
HRR surrogates varies with equivalence ratios. It was found
that using the Miller mechanism, the equivalence ratios
corresponding to the optimal performance of [NH3][OH],
[NH2][O], and [NH2][H] for atmospheric flames are 1.15, 0.95
and 1.05, respectively, while those for high-pressure flames
are 1.11, 0.87 and 0.96, respectively. The results using
different ammonia mechanisms are qualitatively similar. In
summary, these are novel findings that could potentially
contribute to emission control in ammonia combustion and
the flame front identification.
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.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 3 4 6 1 e1 3 4 7 0
Acknowledgments
The authors are grateful for the support of this research by the
National Natural Science Foundation of China (Grant No.
51976185, 52022091).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.01.154.
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