Fuel 361 (2024) 130773

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Full Length Article

Study on lean combustion of ammonia-hydrogen mixtures in a

pre-chamber engine
Jinlu Huo a, Tongbin Zhao b, c, He Lin a, Jinhua Li b, c, Wei Zhang b, c, Zhen Huang a, Dong Han a, *
a
Key Laboratory for Power Machinery and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b
National Engineering Laboratory of Ship and Ocean Engineering Power System, Shanghai 201108, China
c
Shaanxi Diesel Heavy Industry, Xingping Shaanxi 713105, China

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

Keywords: Ammonia holds promise for achieving zero carbon emissions from internal combustion engines. The pre-chamber
Ammonia-hydrogen turbulent jet ignition, characterized by multipoint distributed ignition and rapid combustion, could be applied to
Engine combustion ammonia combustion to extend combustion limits and stability. This study investigates the impacts of hydrogen
Emissions characteristics
energy fraction (Hfrac), equivalence ratio, and ignition timing on the combustion and emission characteristics of
NOx generation mechanism
ammonia-hydrogen mixture at lean combustion conditions in a pre-chamber (PC) marine engine by CFD
Pre-chamber jet ignition
Simulation. In H2-fuel active PC mode, increasing the hydrogen content or achieving stoichiometric combustion
within the PC will shorten the cold jet phase and accelerate the formation of a more intense hot jet. As the Hfrac
and the equivalence ratio in the main-chamber increase, the combustion pressure, temperature, and heat release
rate (HRR) rise, while the combustion duration shortens due to enhanced reactivity, potentially leading to end
gas auto-ignition and knock due to lower auto-ignition energy of the mixture. NO primarily forms near the flame
front, and both NO concentration and the generation area increase with an increase in hydrogen content and
equivalence ratio. Fuel-NO is likely to be the dominant factor in NO generation with lean combustion conditions.
N2O, as a product of NH3 low-temperature combustion, is mainly concentrated near the flame front. An increase
in unburned NH3 emissions corresponds to an increase in N2O emissions. Delaying the ignition timing to reduce
NOx emissions is primarily achieved by controlling NO emissions, even though there is a slight increase in N2O.

1. Introduction However, the employment of zero-carbon fuels in ICEs emerges as an

Internal combustion engines (ICEs) play a crucial role in global
transportation, particularly within the maritime and automotive sectors.
Nevertheless, their dependence on fossil fuels, such as diesel and gaso­
line, has resulted in an escalation in atmospheric carbon dioxide (CO2)
levels, thereby contributing to the global warming effect. To tackle this
challenge, the International Maritime Organization (IMO) introduced a
strategy aiming at mitigating greenhouse gas emissions within the
shipping industry. This strategy endeavors to achieve a 40 % reduction
in carbon intensity by 2030, relative to the levels recorded in 2008,
while attain a remarkable 70 % reduction by 2050 [1]. Consequently, in
recent years, significant efforts have been dedicated to developing so­
lutions for low-carbon and zero-carbon emissions in ship propulsion
within the domain of ICEs [2–6].
Functioning as the energy conversion systems, ICEs contribute to
carbon emissions through the combustion of carbon-based fuels.
efficacious way to address this issue. In the pursuit of alternative fuels
with zero carbon emissions, hydrogen has garnered significant atten­
tion. Hydrogen (H2) is widely recognized as a clean and environment-
friendly fuel since its combustion process only produces water. It can
be produced using renewable and non-renewable methodologies [7].
Hydrogen exhibits favorable characteristics such as rapid flame propa­
gation, high heat value, and a broad flammability range, which can
significantly enhance the ICEs combustion process and improve its
thermal efficiency [8]. Nevertheless, the utilization of hydrogen has
hurdles in the realm of transportation and storage. Moreover, hydrogen
engines may encounter challenges such as backfire, pre-ignition, and
detonation [9,10], which limit their practical application.
In recent years, ammonia (NH3) has emerged as a highly promising
zero-carbon fuel and efficient hydrogen carrier, embodying great po­
tential and playing an important role in the realm of sustainable energy
[11,12]. In comparison to hydrogen, ammonia exhibits enhanced

* Corresponding author.
E-mail address: dong_han@sjtu.edu.cn (D. Han).

https://doi.org/10.1016/j.fuel.2023.130773
Received 22 September 2023; Received in revised form 5 December 2023; Accepted 26 December 2023
Available online 30 December 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
J. Huo et al.
Fig. 1. Engine and pre-chamber model used in the Converge software.
Table 1
Engine specification and boundary conditions.
Parameter
Stroke number 4 from traditional carbon-based fuels are primarily of thermal-NOx,
Bore (mm) 400
Stroke (mm) 520
Compression ratio 11.25
Engine speed (r/min) 500
Intake pressure (bar) 3.3
Intake temperature (K) 323
Exhaust pressure (bar) 3.06
IMEP (bar) 20
compressibility and liquefaction properties, endowing it with a higher
volumetric energy density [13]. Nonetheless, the utilization of ammonia
in ICEs presents distinctive obstacles. It manifests high ignition energy,
slow flame propagation, and a limited flammability range, thereby
giving rise to problems such as cold start difficulties and inadequate
combustion stability when employing pure ammonia. Furthermore, the
nitrogen-containing fuel composition leads to the nitrogen oxides (NOx)
emissions, serving as an additional drawback to ammonia combustion
[14,15]. As a consequence, the exclusive use of ammonia as the primary
fuel in large-scale marine engines faces significant challenges.
The blending combustion of ammonia and hydrogen harnesses the
mutually advantageous effects of their individual combustion charac­
teristics, offering a feasible solution for ammonia-powered ICEs.
Comprehensive experimental results have conclusively demonstrated
that the incorporation of hydrogen brings about remarkable modifica­
tions to the combustion properties of ammonia [16,17]. For instance, as
the hydrogen volume fraction in the ammonia-hydrogen mixtures in­
creases from 0 % to 60 %, the flame propagation velocity of the mixture
at normal conditions escalates from 6.5 cm/s to 66.3 cm/s [18–20].
Mørch et al. [21] investigated the combustion performance of ammonia-
hydrogen mixtures at varied proportions in spark-ignition engines. The
research revealed that the blending of a 5 % volume fraction of hydrogen
resulted in a notable enhancement in the combustion stability of
ammonia in the engine. Similar studies were conducted by Lhuillier
et al. [22] in a spark-ignition engine. The findings pointed out that when
the hydrogen volume fraction surpassed 40 %, the engine exhibited
stable operation at lean combustion conditions with an equivalence
ratio of 0.6. Nevertheless, with the increased ammonia content in the
mixtures, it becomes necessary to advance the ignition timing to
maintain both combustion stability and power output in the engine.
Frigo et al. [23] emphasized the importance of hydrogen addition to
improve the ignition performance of ammonia and increase the com­
bustion rate, with the hydrogen content mainly determined by the en­
gine load. To ensure stable engine power output, the minimum
hydrogen volume fraction should be 7 % at full loads, and this propor­
tion should increase to 11 % at partial loads.
2
Fuel 361 (2024) 130773
As previously mentioned, the blending of hydrogen in ICEs greatly
enhances the ignition and combustion performance of ammonia. How­
ever, several studies have also indicated that the blending of hydrogen
has an adverse impact on the engine NOx emissions. The NOx emissions
generated through extended Zeldovich mechanisms (R1-R3), and the
NOx production rates are dependent on the combustion temperature and
the residence time of nitrogen-species at high temperatures [24]. For
ammonia-hydrogen mixtures, in addition to the Zeldovich pathways,
NOx emissions may primarily originate from the process of ammonia
dehydrogenation and oxidation, commonly referred to as fuel-NOx [25].
N + OH = NO + H (R1)
N + O2 = NO + O (R2)
N + NO = O + N2 (R3)
The research conducted by Lhuillier et al. [22] illustrates that the
NOx emissions from ammonia engines were influenced by the hydrogen
blending ratio and equivalence ratio. To enhance the combustion rate of
ammonia at lean conditions, the hydrogen volume fraction was
increased from 10 % to 60 %, resulting in an elevation of NOx emissions
from 4000 ppm to 9000 ppm. The introduction of hydrogen raised the
flame combustion temperature, thus promoting the formation of ther­
mal-NOx. In comparison to stoichiometric and rich conditions, NOx
emissions were higher with lean combustion conditions, reaching a peak
at an equivalence ratio of ~0.8 [22]. Mørch et al. [21] also investigated
the impact of hydrogen content and excess air ratio on NOx emissions,
and found that the highest NOx emissions were produced when the
percentage of hydrogen exceeds 20 % and the excess air ratio was within
the range of 1.1 to 1.4, consistent with the findings of Lhuillier et al.
[22].
To regulate the generation of NOx in the ammonia-hydrogen blended
combustion, a study was conducted by Pandey et al. [26]. This study
explored the influences of ignition timing and exhaust gas recirculation
(EGR) on NOx emissions in ammonia-hydrogen mixtures, with a
hydrogen volume fraction of 30 % and an excess air ratio of 1.1. The
findings revealed that advancing the ignition timing led to an initial
decrease followed by an increase in the engine combustion duration.
Simultaneously, NOx emissions exhibited an initial rise followed by a
decline. Furthermore, by increasing the EGR rate up to 25 %, the peak
combustion temperature decreased, leading to a substantial reduction of
45 % in NOx emissions.
Literature review suggests that exerting control over the hydrogen
blending ratio and equivalence ratio may contribute to mitigate the NOx
emissions. Although NOx emissions can be controlled at lower levels
with stoichiometric or rich operation conditions, the increased heat
transfer losses and incomplete combustion have resulted in a reduction
of thermal efficiency [27]. Exploring ammonia-hydrogen ultra-lean
combustion has the potential to achieve high thermal efficiency and low
J. Huo et al.
Fig. 2. Natural gas engine model validation.
NOx emissions. However, an over-lean fuel–air mixture leads to com­
bustion instability and even misfire, especially for ammonia fuel. As a
result, the practice of lean combustion imposes high demands on the
engine ignition system. The conventional spark ignition, with limited
ignition energy and single-point flame propagation, is not suitable for
lean combustion in large-bore marine engines. The pre-chamber (PC)
turbulent jet ignition (TJI) utilizes the injection of high-temperature
gases enriched with hydrogen radicals into the main-chamber (MC),
which generates multiple ignition sources and induces strong turbulence
[28–30]. As a result, the low-reactivity mixture in the MC is ignited,
achieving stable and dependable ignition performance. Hence, the PC-
TJI mode make it possible to achieve ultra-lean combustion of
ammonia-hydrogen mixtures. Moreover, compared to the passive PC
without fuel injection, the active PC mode could further extend the lean
combustion limit by an auxiliary fuel supply system. Considering that
3
Fuel 361 (2024) 130773
the hydrogen is characterized by fast flame propagation speed and high
adiabatic flame temperature, ultra-lean combustion of ammonia-
hydrogen can be achieved with H2-fueled active PC engine. In addi­
tion, there is potential to further reduce the energy substitution rate of
hydrogen in H2-fueled active PC mode.
However, there are still limited researches on the ignition of lean
ammonia-hydrogen mixtures using PC-JTI. Additionally, the influence
of hydrogen blending ratio and equivalence ratio on NOx emissions from
ammonia-hydrogen mixtures still require further exploration. Therefore,
this study numerically investigates the combustion and emissions
characteristics of ammonia-hydrogen in H2-fueled active PC marine
engines at fuel lean conditions. The impact of hydrogen blending ratio,
equivalence ratio, and ignition timing on the ammonia-hydrogen com­
bustion and NOx emissions of ammonia engines is analyzed.
J. Huo et al. Fuel 361 (2024) 130773

Fig. 3. Comparison between measured and predicted laminar flame speed results.

range of 2.11 to 3.65 bar, was constructed in the GT-ISE/GT-Power

Table 2 software [32]. The 1D model utilized normalized combustion rate data
Calculation conditions. provided by the engine manufacturer to simulate the engine steady-state
Section Hydrogen energy Equivalence ratio Ignition timing operation, thereby providing boundary conditions and initial conditions
fraction (Hfrac) (φ) for the 3D simulation. Table 1 presents the parameters of the base engine
1 10 %–40 % 0.5 − 8 ◦ CA ATDC and the boundary conditions used for numerical simulation. The high
2 20 % 0.4/0.5/0.6 − 8 ◦ CA ATDC power and torque requirements of marine engines necessitate lower
3 20 % 0.5 12/− 10/− 8/− 6/
−
rotational speeds compared to conventional gasoline and diesel engines.
− 4 ◦ CA ATDC
Therefore, this study selected the common operating speed of 500 r/min
and full-load conditions for investigation.
2. Methodology For the ammonia-fueled engine, its operation mode was similar to
that of the natural gas engine. The engine intake manifold received an
2.1. Model description injection of ammonia-hydrogen premixed gas, which blends with air to
form a homogeneous mixture that enters the combustion chamber. After
The three-dimensional (3D) computational fluid dynamics (CFD) the PC spark ignition during the compression stroke, pressure built up
model of a natural gas engine was established using the CONVERGE 3.0 within the PC, forcing the expulsion of the cold fuel–air mixture and hot
software [31]. The geometric model included structures such as the products through nozzles.
intake system, exhaust system, cylinder, and pre-chamber, as shown in In this study, the SAGE model, which can be combined with detailed
Fig. 1. The pre-chamber features six jet orifices, and at the top dead chemical reaction kinetics mechanisms, was selected for the combustion
center, the volume ratio between the pre-chamber and the main- model [33]. The re-Normalization Group (RNG) k-ε model was chosen
chamber is approximately 0.8 %. Additional fuel can be injected into for the turbulence model [34]. The basic grid size was set at 14 mm, and
the pre-chamber through the fuel injection ports located at the upper the minimum grid size was 0.875 mm. Additionally, the Adaptive Mesh
part of the pre-chamber. Additionally, a 1D engine model with waste Refinement (AMR) was configured in the important regions with high
gate turbocharger, which is capable of realizing intake boost within the velocity gradients and high temperature gradients. The maximum

4
J. Huo et al. Fuel 361 (2024) 130773

Fig. 4. Predicted distributions of hydrogen and equivalence ratio (at − 8 ◦ CA ATDC) with different hydrogen fractions.

Fig. 5. Comparison of jet velocity and OH transport between the PC and the
MC with different hydrogen fractions.

number of grids used in the calculation process was 9.5 million, and grid
independence verification was conducted.

2.2. Model validation

In the pre-chamber jet ignition mode, a comparison between the 3D

simulation results using the natural gas GRI 3.0 mechanism [35] and the
1D calculation results is presented in Fig. 2. It can be observed that the
cylinder pressure obtained from the 3D simulation closely aligns with
the 1D simulation results at different engine loads. The accuracy of the
3D model and parameter settings are verified, which can support the
following flow and combustion performance studies of the ammonia-
fueled marine engine.
Fig. 6. Cylinder pressure (a), temperature (b) and HRR (c) with different
hydrogen energy fractions.
2.3. NH3/H2 reaction mechanism
A detailed chemical reaction mechanism is essential for combustion
simulations. Several researchers, including Otomo et al. [36], Han et al.
[37], and Stagni et al. [38], have developed NH3/H2 combustion

5
J. Huo et al. Fuel 361 (2024) 130773

model, Han-model, and Stagni-model for laminar flame speeds were

compared with the experimental results of Lhuillier et al. [18], as shown
in Fig. 3. Among different conditions, the Stagni model provides more
reasonable prediction for the experimental results. Therefore, we adopt
the NH3/H2 combustion mechanism developed by Stagni et al. [38],

Fig. 7. Combustion phase and duration with different hydrogen en­

ergy fractions.

reaction mechanisms. However, different mechanisms exhibit signifi­

cant differences in predicting experimental outcomes. In the premixed
combustion mode, the predictive accuracy of laminar flame speed is
particularly important. Therefore, the prediction results of the Otomo- Fig. 9. NH3 and NOx emissions with different hydrogen energy fractions.

Fig. 8. The distributions of temperature with different hydrogen fractions.

6
J. Huo et al.
Fig. 10. The variation of NO and N2O production with different hydrogen
energy fractions.
which contains 31 species and 203 reactions.
2.4. Calculation conditions
Regarding the H2-fueled active PC engine, the PC jet flame feature is
significantly affected by hydrogen injection mass and the mixture in the
MC. This study primarily focuses on the effect of MC pre-mixed gas on
engine performance in the H2-fueled active PC mode. Therefore, the
hydrogen injection mass is maintained at 0.009 g, and the PC global
equivalence ratio is 0.74 at ignition timing. The effect of hydrogen in­
jection mass on the PC jet flame will be explored in subsequent research.
The ammonia-hydrogen blended combustion calculation conditions
are presented in Table 2. The hydrogen blending ratio is defined as the
proportion of energy contributed by hydrogen in the ammonia-
hydrogen mixture, calculated as follows:
mh • LHV h
Hfrac =
mh • LHV h + ma • LHV a
where Hfraction is the hydrogen energy blending ratio, and for example
7
Fuel 361 (2024) 130773
H10 indicates that the hydrogen energy is 10 % of that of the mixture;
mh and ma represent the mass of hydrogen and ammonia in the mixture,
respectively; the lower heating value of hydrogen, LHVh, is 120 MJ/kg,
and the lower heating value of ammonia, LHVa, is 18.8 MJ/kg [22].
2.5. Emissions analysis
In this study, the emissions of pollutants are assessed using indicated
specific NOx emissions (IS-NOx) and indicated specific NH3 (IS-NH3)
emissions. The calculation formula is as follows:
mNOx
IS − NOx =
Pmi × V
mNH3
IS − NH3 =
Pmi × V
where Pmi is the indicated mean effective pressure, V is the engine
displacement, mNOx is the emission mass of NOx, and mNH3 is the
emission mass of NH3.
3. Results and discussion
3.1. Effect of hydrogen energy fraction on combustion and emissions
For H2-fueled active PC engine, the PC jet flame dominates the
ignition and combustion processes within the MC. Therefore, the dis­
tributions of hydrogen and equivalence ratio within the PC are
compared first with different MC hydrogen blending ratios, as shown in
Fig. 4. As the MC hydrogen energy fraction increases, the hydrogen
concentration within the PC gradually rises, forming hydrogen enrich­
ment near the spark plug. Despite no significant differences in the PC
equivalence ratio, the increase in the proportion of hydrogen will pro­
mote ignition and flame propagation due to higher flame propagation
speed compared to ammonia. After spark plug ignition, the PC jet un­
dergoes two phases: from cold jet to hot jet [39]. As a highly reactive
radical, the transport of OH between the PC and the MC can be used to
indicate that the flame front has propagated into the MC, signifying the
formation of the hot jet. Moreover, during the period from the formation
of jet to the onset of OH transport, the PC jet is referred to as the cold jet,
characterized by the propagation of the flame front within the PC. Fig. 5
compares the differences in PC jets between different cases by exam­
ining jet velocity and the transport of OH. As the hydrogen energy
fraction increases, the shortened cold jet period and the early appear­
ance of the hot jet are observed. This is because the increase in hydrogen
concentration accelerates the PC flame propagation. Therefore, a highly
reactive PC gas atmosphere is favorable for the formation of jet flames.
To clarify the effects of hydrogen energy fraction on the combustion
characteristics of ammonia engine, cylinder pressure, temperature and
heat release rate (HRR) with different Hfrac are analyzed as depicted in
Fig. 6. It is found that with the increase of Hfrac, the peak values of in-
cylinder pressure, temperature and HRR increase. Moreover, an abnor­
mally increased HRR is observed when the Hfrac is equal to 40 %. This is
because, as the hydrogen energy substitution rate increases, the reac­
tivity of the in-cylinder mixture and the chamber temperature are
enhanced, leading to the end-gas auto-ignition during past-combustion
phase. In the H2-fueled active PC mode, the hydrogen blending ratio
should be kept below 40 % to avoid engine knock. However, when Hfrac
is equal to 10 %, the MC peak pressure is only 9.3 MPa, indicating that a
higher energy substitution rate is necessary to ensure rapid combustion
of ammonia with lean combustion condition. Fig. 7 compares the com­
bustion phase and duration with different hydrogen blending ratios. It
can be observed that the CA50-90 period is most significantly influenced
by the hydrogen energy faction. During this period, the combustion
process within the MC is primarily dominated by turbulent flame
propagation. The slow flame propagation speed leads to an extension of
the CA50-90 period when Hfrac is equal to 10 %. Fig. 8 shows the
J. Huo et al. Fuel 361 (2024) 130773

Fig. 11. Temperature (left) and NO (right) distribution with different hydrogen energy fractions.

Fig. 12. Temperature (left) and N2O (right) distribution with different hydrogen energy fractions.

development and evolution of the jet flame with different hydrogen
energy fractions. The upper part shows the temperature distribution,
and the lower part is a top-down view of the 1600 K isothermal surface.
Due to the higher adiabatic flame temperature of hydrogen compared to
ammonia, as the proportion of hydrogen in the MC increases, the jet
flame temperature shows an increasing trend.
Unburned NH3 and NOx are the main pollutants of ammonia engine
emissions. Fig. 9 shows the comparisons of NH3 and NOx emissions with
different hydrogen fractions. At a 10 % hydrogen energy fraction, the
unburned NH3 emissions amount to 31.5 g/kWh. This is related to the
inadequate flame propagation capability and lower combustion tem­
perature during the post-combustion phase, leading to a significant
amount of unburned ammonia. When the hydrogen energy fraction in­
creases to above 20 %, unburned ammonia emissions decrease signifi­
cantly and reach zero level due to the increased flame propagation speed
and combustion temperature. Regarding to NOx emissions, NOx

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J. Huo et al. Fuel 361 (2024) 130773

Fig. 13. Predicted distributions of hydrogen (left) and equivalence ratio (right) with different equivalence ratios.

typically consists of NO, NO2, and N2O. In hydrocarbon fuels, the pri­
mary components of NOx emissions are NO, with smaller contributions
from NO2 and N2O. For ammonia fuels, the primary components of NOx
may vary due to the presence of fuel-N. As depicted in Figs. 9, N2O
makes a substantial contribution to NOx emissions with 10 % hydrogen
addition, and the greenhouse effect caused by N2O is 298 times greater
than that of CO2 [38]. As the hydrogen energy fraction increases, N2O
emissions decrease, while NO emissions increase rapidly, becoming the
predominant component of NOx. The changes in N2O and NO exhibit
completely opposite trends, which also implies that when N2O increases,
NO decreases.
Furthermore, the variations of NO and N2O production with crank
angle are thoroughly analyzed, and the NO generation at CA50 and
CA90 timings is labeled, as shown in Fig. 10. In Fig. 10(b), it is observed
that the production of NO initially increases and then exhibits a down­
trend during the expansion stroke. As the hydrogen blending ratio in­
creases, the peak and growth rate of NO gradually increase, and the NO
peak value exceeds 20 g/kWh when Hfrac is equal to 40 %. NO is

Fig. 14. Comparison of jet velocity and OH transport between the PC and the MC with different equivalence ratios.

9
J. Huo et al. Fuel 361 (2024) 130773

Fig. 17. NH3 and NOx emissions with different equivalence ratios.

generated through ammonia oxidation and thermal pathways, and

Fig. 15. Cylinder pressure (a), temperature (b) and HRR (c) with different
equivalence ratios.
thermal-NO is highly sensitive to combustion temperatures. Neverthe­
less, after the CA90 moment, reaching the peak temperature does not
lead to an increase in NO production, indicating that thermal pathways
play a secondary role in NO generation when the Hfrac is less than 20 %.
When the Hfrac continues to rise, more OH/H radicals and higher in-
cylinder combustion temperatures are achieved, leading to increased
production of both fuel-NO and thermal-NO. The cylinder temperature
and NO distribution depicted in Fig. 11 also confirm these conclusions.
The temperature and NO distribution on the left side cross-section are
arranged in a mirrored symmetric pattern. It can be observed that the
combustion temperature at the core of the jet flame is highest, and as
such NO primarily forms near the flame front rather than in the high-
temperature region, highlighting the significant role of fuel pathways
in NO generation. In other words, when Hfrac increases from 10 % to 40
%, NO emissions increase, which is likely primarily attributed to the fuel
pathways. In the PC, the high hydrogen content and elevated combus­
tion temperature result in a concentrated NO distribution. However, due
to the significantly limited volume of the PC, the generated NO has
minimal impact on engine emissions. The consumption of NO is attrib­
uted to thermal De-NOx reactions, which primarily occur within the
narrow temperature range of 1100–1400 K [40]. At the later stage of
combustion, unburned ammonia in the cylinder undergoes hydrogen
extraction reactions with O/OH to produce NH2/NH (R4-R5). After­
wards, NH2/NH reacts with NO by thermal De-NOx reactions (R6-R8),
resulting in the consumption of NO [41].

NH3 + OH = NH2 + H2O (R4)

NH3 + O = NH2 + OH (R5)

NH2 + NO = NNH + OH (R6)

NH2 + NO = N2 + H2O (R7)

NH + NO = N2O + H (R8)

As seen in Fig. 10(b), N2O, as a product of ammonia oxidation,

rapidly increases by the reaction (R9-R10) at the beginning of com­
bustion, after which N2O undergoes thermal decomposition (R9), lead­
ing to a decrease in N2O concentration. It should be noted that the
Fig. 16. Combustion phase and duration with different equivalence ratios.
reaction (R9-R10) typically occurs within the temperature range of

10
J. Huo et al.
Fig. 18. NO (a) and N2O (b) emissions with different equivalence ratios.
900–1300 K, and as the temperature continues to increase, N2O de­
composes to form stable N2 via R11 [42,43]. Therefore, the production
area of N2O is mainly the low temperature area where ammonia reacts,
and it hardly exists in the high temperature area, as shown in Fig. 12.
When ammonia undergoes incomplete combustion at lower tempera­
tures, the generation of N2O is promoted, while N2O thermal decom­
position is inhibited. This explains why the N2O emissions are relatively
high and experience a slightly increase during the expansion process
with 10% hydrogen addition.
NH2 + NO2 = N2O + H2O
NH + NO = N2O + H
N2O (+M) = N2 + O (+M)
3.2. Effects of equivalence ratio on combustion and emissions
Fig. 13 shows the distribution of hydrogen and equivalence ratio
Fuel 361 (2024) 130773
within the PC at different equivalence ratios. An increase in the intake
charge equivalence ratio leads to more fuel being compressed into the
PC during the compression stroke. Therefore, fuel enrichment occurs
near the spark plug with the increased intake charge equivalence ratio.
As expected, the PC jets are formed at an earlier stage, and jet velocity
increases as the PC equivalence ratio converts from lean to rich condi­
tions, as shown in Fig. 14.
Fig. 15 illustrates cylinder pressure, temperature and HRR with
different equivalence ratios. With an increase in the equivalence ratio,
the cylinder peak pressure temperature and heat release rate gradually
increase. This general trend is expectable, with an increase in the
equivalence ratio, more fuel is introduced into the cylinder, thereby
enhancing the reactivity of the mixture and resulting in a stronger
combustion intensity. As the equivalence ratio increases from 0.4 to 0.7,
the flame propagation speed accelerates, and the combustion duration
significantly shortens, with CA50-90 reducing from 21.5 ◦ CA to 3.9 ◦ CA,
as shown in Fig. 16.
Fig. 17 compares the NH3 and NOx emissions with different equiv­
alence ratios. At an equivalence ratio of 0.4, unburned NH3 emissions
are the highest, corresponding to elevated N2O emissions. As mentioned
earlier, N2O is a product of ammonia low-temperature combustion, and
a substantial amount of unburned ammonia emissions imply low com­
bustion temperatures and available NH/NH2 radicals, which provide the
conditions for N2O formation. With an increase in equivalence ratio, the
reactivity of the mixture increases, effectively curbing the unburned
NH3 emissions, consequently leading to a significant reduction in N2O
emissions.
Fig. 18(a) shows the variation curve of NO with different equivalence
ratios. At an equivalence ratio of 0.4, the NO production remains
consistently at a low level and primarily concentrates near the flame
front, as shown in the Fig. 19. Therefore, when the mixture is extremely
lean, the low in-cylinder combustion temperature results in NO pri­
marily generated through fuel pathways. As the equivalence ratio in­
creases to 0.6, NO first forms near the flame front, and then expands
toward the jet flame core with the increase in combustion temperature.
A possible reason is that the increased combustion temperature and the
prolonged high-temperature duration promote the formation of
thermal-NO, which is also reflected in the increase in NO after CA90.
Fig. 18(b) shows the variation curve of N2O with different equiva­
lence ratios. Firstly, it can be observed that when the equivalence ratio is
0.4, N2O consistently shows a gradual increasing trend, reaching a final
emission level of 13.7 g/kWh. This is because excessively lean condi­
tions lead to a significant reduction in combustion temperature, as
shown in Fig. 20. Low-temperature combustion (below 1400 K) pro­
motes the formation of N2O through R9 - R10 and inhibits the decom­
position of N2O. As the mixture becomes richer, the N2O concentration
significantly decreases due to the increase in combustion temperature.
3.3. Effect of ignition timing on combustion and emissions
Fig. 21 shows cylinder pressure, temperature and HRR with different
ignition timings. As the ignition timing is delayed, the peak pressure,
temperature, and heat release rate in the cylinder gradually decrease.
The delay in the ignition timing postpones the heat release process,
causing more heat to be released during the piston downward move­
ment, thereby reducing the proportion of constant volume combustion.
(R9)
As a result, the peak pressure will decrease, which corresponds to the
(R10) delayed combustion center (CA50), as shown in Fig. 22. The delay in
ignition timing has a notable impact on the CA50-90 period, and also
(R11) leads to an increase in temperature during the expansion process due to
the delayed heat release, as shown in Fig. 21(b).
Fig. 23 compares the NH3 and NOx emissions with different ignition
timings. As the ignition timing is altered, a trade-off between NH3 and
NOx emissions becomes evident. As the ignition timing is delayed to
− 4 ◦ CA ATDC, unburned NH3 emissions increase to 2.96 g/kWh, while
NOx emissions decrease to 0.61 g/kWh. When the ignition timing is
11
J. Huo et al.
Fig. 19. Temperature (left) and NO (right) distribution with different equivalence ratios.
Fig. 20. Temperature (left) and N2O (right) distribution with different equivalence ratios.
advanced to − 12 ◦ CA ATDC, NH3 emissions are nearly zero, but NOx
emissions increase to 14.3 g/kWh.
The variations of NO with crankshaft angle at different ignition
timings are shown in Fig. 24(a), with the NO generation at CA50 and
CA90 timings labeled. At CA50, there is only a slight difference in the
NO generation at different ignition timings. As the ignition timing is
advanced, the NO generation during the CA50-90 period significantly
increases, and this increase trend continues after CA90. Based on the NO
distribution at CA90 as depicted in Fig. 25, it can be observed that the
NO concentration and distribution area near the flame front gradually
increase with the advanced ignition timing. The phenomenon of
decreasing NO concentration from 40 ◦ CA ATDC to 60 ◦ CA ATDC is not
pronounced, with the advancement of ignition timing. This phenome­
non can be explained as follows. As shown in Fig. 25, the increased in-
cylinder combustion temperature is observed, achieved by advancing
ignition timing, which promotes the generation of NO through the
thermal pathway in the post-combustion zone. On the other hand, the
NO generation at the flame front gradually increases with the rise in
flame temperature. More importantly, during the expansion process, an
12
Fuel 361 (2024) 130773
advanced ignition timing suppresses the De-NOx effect. This is because
ammonia oxidation is promoted, reducing the availability of NH₂/NH.
Combining Fig. 23 and Fig. 24(b), it is evident that as ignition timing
is delayed, there is a slight increase in N2O, eventually becoming the
dominant component of NOx when the ignition timing is at − 4 ◦ CA
ATDC. The increase in N2O generation is primarily attributed to the
reduction in flame temperature, which promotes the R9-R10 reaction
and inhibits N2O decomposition. Moreover, delaying the ignition timing
to reduce NOx emissions is primarily achieved by controlling NO emis­
sions, even though there is a slight increase in N2O.
4. Conclusions
The performance of an ammonia-hydrogen combustion engine with
H2-fuel active PC ignition system was investigated based on numerical
simulation. The effects of hydrogen energy fraction, equivalence ratio
and ignition timing on the combustion and emission characteristics of
ammonia-hydrogen mixture with lean combustion conditions were
studied. The main conclusions are as follows:
J. Huo et al. Fuel 361 (2024) 130773

Fig. 21. Cylinder pressure (a), temperature (b) and HRR (c) with different ignition timings.

Fig. 23. NH3 and NOx emissions with different ignition timings.
Fig. 22. Combustion phase and duration with different ignition timings.

13
J. Huo et al.
Fig. 24. NO (a) and N2O (b) emissions with different ignition timings.
(1) High-temperature hot jets with high turbulence energy play a
critical role in the rapid combustion of lean mixtures. Increasing
the hydrogen content or transitioning the PC operation condi­
tions from lean to stoichiometric shortens the cold jet phase,
accelerates the formation of a more intense hot jet, and conse­
quently initiates the MC combustion process earlier.
(2) Increasing the Hfrac and the equivalence ratio of the MC mixture
results in higher combustion pressure, temperature and HRR,
while shortens the combustion duration due to the enhanced
reactivity of the mixture. However, in the H2-fuel active PC-TJI
mode, the increased reactivity of the mixture raises the ten­
dency for end gas auto-ignition and knock due to lower mixture
auto-ignition energy.
(3) As both Hfrac and the equivalence ratio increase, there is an up­
ward trend in NO production. Furthermore, NO is primarily
generated at the flame front through fuel pathways. During the
expansion stroke, NO can be consumed through thermal De-NOx
reactions, but this is contingent upon the combustion tempera­
ture and the availability of NH/NH2.
14
Fuel 361 (2024) 130773
(4) N2O, a product of ammonia low-temperature oxidation, is
generated through the reactions (NH2 + NO2 = N2O + H2O, NH
+ NO = N2O + H) at temperatures below 1400 K, and is subse­
quently converted into stable N2 at high temperatures. This
characteristic determines that N2O is distributed in the flame
front, and as the flame temperature increases, N2O generation is
suppressed.
(5) By delaying spark ignition, the in-cylinder heat release process is
postponed, resulting in a reduction in in-cylinder pressure and
temperature, and an extended combustion duration. Moreover,
the NOx emissions reduction through delayed ignition timing is
primarily achieved by NO emissions control, in spite of a slight
increase in N2O.
CRediT authorship contribution statement
Jinlu Huo: Writing – original draft, Methodology, Investigation,
Formal analysis, Data curation. Tongbin Zhao: Resources, Investiga­
tion. He Lin: Resources, Investigation. Jinhua Li: Resources. Wei
Zhang: Resources. Zhen Huang: Supervision, Resources. Dong Han:
J. Huo et al.
Fig. 25. Temperature (left) and NO (right) distribution with different ignition timings.
Writing – review & editing, Visualization, Supervision, Resources,
Conceptualization.
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.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work is supported by National Key Research and Development
Program (Grant No. 2022YFE0209000), National Natural Science
Foundation of China (Grant No. 52022058) and Science and Technology
Commission of Shanghai Municipality (Grant No. 22170712600).
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