Fuel 360 (2024) 130617

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Study on the impact mechanism of ammonia energy fraction on in-cylinder

combustion and pollutant generation under wide operation conditions of
medium-speed diesel engines
Yejian Qian a, Yu Sun a, *, Zhen Gong a, *, Shun Meng a, Xiaofei Wei a, Binbin Tang b, Juye Wan a
a
School of Automotive and Transportation Engineering, Hefei University of Technology, No.193 Tunxi Road, Hefei, Anhui 230009, China
b
An Qing CSSC Diesel Engine Co., Ltd., Anqing 246003, China

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

Keywords: To expedite the utilization of ammonia in the domain of marine medium-speed diesel engines. The computa­
Ammonia tional fluid dynamics (CFD) model combined with the ammonia/n-dodecane reaction mechanism were con­
Energy ratio ducted to explore the impact mechanism of ammonia energy ratio (AER) and diesel injection timing on in-
Combustion
cylinder combustion and pollutant emission at low-mid-high loads of marine medium-speed diesel engines.
Dual-fuel engine
Further, the formation laws of Thermal and Fuel nitrogen oxides (NOX) at various AER conditions were analyzed.
NOx
At 10 % load, the rising AER advanced the CA50 by 57 % and increased the in-cylinder peak pressure by 3.5 %
due to the enhanced premixed combustion stage. Whereas, at higher loads (50 % & 100 %), the effect of high
specific heat capacity of ammonia played a crucial role in combustion progress with the increasing AER, which
reduced the in-cylinder peak pressure by 1–3 %. The sensitivity of key combustion phases (CA10-CA90) to AER
also gradually decreased with the rising loads because of the inhibited diffusion combustion stage. When the IT
was 6◦ BTDC, the peak temperature in the cylinder decreased by 10 % at 10 % engine load; and the charge of
excessive temperature in the cylinder was significantly reduced at 50 % and 100 % engine load. In terms of
emission characteristics, HC and CO emission significantly reduced when AER was 45 %. And the proportion of
Fuel NH3 in the fuel rose from 75.5 % to 91.4 % with the increasing AER. This means that the generation
conditions of Thermal NOx were inhibited in the large proportion of ammonia-doped combustion conditions.

more attention from researchers.

1. Introduction
As a major area of energy consumption, the internal combustion
engine has a particularly urgent need for alternative fuels. In recent
years, many researches concentrated on alternative fuels such as
hydrogen (H2), methanol (CH3OH), and ammonia (NH3). Hydrogen
energy is a clean energy source that has received a lot of attention
recently, but hydrogen remains a major challenge in the transportation
and utilization process due to its low boiling point (− 252 ℃) and too
wide combustion concentration limits (4–75 %) [1]. Methanol as an
alternative fuel has been more widely studied and applied in marine
engines. although it is easy to transport, the lower calorific value, low
flash point [2] and lower actual fuel replacement ratio (30 %) [3] have
limited its application scope. Meanwhile, the methanol contains carbon
element, the combustion process can easily generate carbon dioxide.
Therefore, ammonia as carbon-free alternative fuel [4] has received
In the 1960s, the U.S. Army began researching the application of
ammonia as alternative fuel on compression-ignition (CI) engines [5].
Conventional CI engines can use ammonia as fuel after minor modifi­
cation [6], this reduces the economic cost in application. Ammonia
appears as a gas state at room temperature. The high compressibility and
low freezing point (− 77.73 ℃) of ammonia also significantly enhance its
transportability, storability and applicable operation ranges is easily
compressed into a liquid state, making it easy to transport and store; The
freezing point of − 77.73 ℃ makes ammonia available for a wider range
of conditions [7]. Further, the ammonia can be adopted as the alterna­
tive fuel in spark-ignition engines because of its high octane number
(>111) and excellent anti-knock properties [8]. However, the combus­
tion efficiency and operating stability of SI engine are lower than CI
engine. Walter et al [9] had already clarified the importance of
researching the CI engine based on ammonia fuel in their early studies.
Toyota demonstrated an ammonia-fueled car in 2013, and MAN, a

* Corresponding authors.
E-mail addresses: qianyjian@163.com (Y. Qian), sunyu_academic@163.com (Y. Sun), 18856072762@163.com (Z. Gong).

https://doi.org/10.1016/j.fuel.2023.130617
Received 12 October 2023; Received in revised form 18 November 2023; Accepted 11 December 2023
Available online 16 December 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
Y. Qian et al.
Nomenclature
Abbreviations
AER Ammonia energy ratio
CFD Computational fluid dynamics
NO Nitric oxide
PFP Peak fire pressure
BTDC Before top dead center
SOI Start of injection
BTDC Before Top Dead Center
CI Compression ignition
NH3 Ammonia
NO2 Nitrogen dioxide
N2O Nitrous oxide
SCR Selective catalytic reduction Reducyion
IT Injection timing
ABDC After Bottom Dead Center
German company, planed to develop ammonia engines to replace LPG
engines used in the marine engine industry [10]. More and more in­
stitutions and scholars pay attention to the research of new engines
based on ammonia fuel.
The research works of engine based on ammonia fuel can be divided
into two stages: pure ammonia-fuel and dual-fuel [11]. The control
system and fuel supply system of pure ammonia engine is more
simplifier than that of dual-fuel engine. The crucial problems of pure
ammonia engine, including high auto-ignition temperature of the fuel,
narrow combustion equivalent ratio and low burning velocity, emerged
during the research [4], are the same as that of natural gas engines.
During the previous studies of pure ammonia-fuel engines, researchers
found that ammonia combustion could be observed only by increasing
the compression ratio of the engine to between 35 and 100 [12,13],
whereas, the compression ratio of conventional diesel engines is only
between 12 and 24 [14], and this obviously does not reach the practical
use conditions. That is why the first stage of ammonia engine research is
stalled for a longer period of time. In recent years, the utilization of
carbon-free fuels has gained attention due to the serious pollution
problems of hydrocarbon fuels and concerns about the depletion of
natural resources. The development of internal combustion engines
based on ammonia fuels has received renewed attention. Based on the
results of the first stage of researches, some researchers have found that
ammonia can operate at lower compression ratios when used as a sec­
ondary fuel in combination with other high-energy fuels [15]. The
combination of NH3 with diesel [13,16], DEM [17,18], hydrogen
[19,20], Dimethyl hydrazine [13,21] or other alternative fuels have
been studied accordingly. Combined with the actual use, diesel, as the
most popular traditional fuel with the most mature industry chain
development, its combination with ammonia is currently the most
concerned research direction.
The NH3/diesel mixed combustion mode can be categorized into
direct injection (DI) and port fuel injection (PFI) based on the method of
NH3 delivery. Burwell et al [22] found that liquid ammonia has a high
latent heat of vaporization, and when ammonia injected the cylinder
directly in liquid form, it could cause a large disturbance to the in-
cylinder temperature and combustion process. Scharl et al [23] stud­
ied the combustion of liquid ammonia by rapid compression expansion
machine (RCEM), in the process of liquid ammonia direct-injection, the
in-cylinder wall quenching effects were notable in liquid ammonia
direct injection process. Gray et al [13] conducted a detailed study about
the ammonia direct injection supply system of engine. The results illu­
minated that the stable in-cylinder combustion process could only be
achieved if ammonia was injected before 80◦ BTDC. In addition, the
technology for specific in-cylinder injectors for ammonia is not yet
2
Fuel 360 (2024) 130617
mature. Therefore, the impact of ammonia supply mode on engine
operation under low pressure is currently a focal point of research. For
example, Niki et al. [24] realized the 18 % energy supply of ammonia by
the PFI supply method, and the participation of ammonia delayed the
ignition time in the cylinder. Tay et al. [21] achieved a 60 % ammonia
energy utilization rate on a diesel engine with a compression ratio of
18.5 through port fuel injection (PFI), and observed the primary and
secondary heat release within an engine cycle. Li et al.[25] investigated
the impact of ammonia on in-cylinder combustion during ammonia/
diesel dual-fuel combustion, considering both direct injection (DI) and
port fuel injection (PFI) modes. Their findings revealed that supplying
ammonia through PFI exhibited a substantial enhancement in the en­
gine’s indicated thermal efficiency. However, according to research re­
sults from Lasocki et al.[26], the impact of ammonia supply in the form
of PFI on combustion is closely related to engine cylinder diameter and
displacement.
The diesel-DI/ammonia-PFI mixed combustion mode is normally
adopted in low-mid speed marine engines due to the restriction of slow
laminar flame propagation speed and long auto-ignition delay time of
ammonia [27]. These engines, which have relatively stable rotation
speed and operation condition, large cylinder bore and long duration per
cycle, can mitigate the drawbacks of the specific ignition properties of
ammonia. Therefore, some studies about the ammonia/diesel dual-fuel
marine engines have been investigated. Zhu et al. [28] achieved
ammonia/diesel composite combustion in the form of PFI on two-stroke
large-diameter marine diesel engines. It has been observed that an in­
crease in the ammonia ratio leads to a lengthening of the ignition delay
time, resulting in intensified premixed combustion. Zhou et al. [29]
investigated ammonia premixed combustion in a cylinder using a low-
speed marine engine as model, and demonstrated that this surrogate
could achieve a thermal efficiency exceeding 50 %. Recently, MAN
Company [30] has also unveiled its long-term strategy for utilizing
ammonia as an alternative fuel in their low- and medium-speed diesel
engines. These findings indicate that the combustion mode of ammonia/
diesel in marine diesel engines merits further investigation.
The pollutant emissions is a crucial problem in the application of
ammonia/diesel mixed combustion mode. The sluggish combustion rate
of ammonia significantly impacts cylinder efficiency, leading to an in­
crease in pollutant emissions. For example, When the energy share of
ammonia reached up to 30 %, Niki et al.[28] found the amount of NOx
and slipped NH3 increased, while CO2 emissions decreased；In a
comparison between ADDF engines and pure diesel engines by Reiter et
al[29]. when the energy ratio of ammonia supply was between 40 % and
60 %, the same effect as that of pure diesel fuel could be achieved, but
with higher levels of CO and HC in the exhaust emissions. Although the
participation of ammonia has an impact on in-cylinder combustion, the
detrimental effects can be mitigated or eliminated through relevant
optimization efforts. Yousefi et al. [30]achieved a reduction in HC and
CO emissions by adjusting the injection timing of pilot fuel. Nadimi et al.
[31]achieved a reduction in PM and CO emissions through the optimi­
zation of the ammonia to diesel ratio. Currently, NOx emissions serve as
the primary pollutant source of compression ignition engines, and the
International Maritime Organization has also implemented stringent
regulations pertaining to NOx emissions[32]. For NOx emission, Niki et
al [33] found fuel injected in the middle and late stage of combustion
reduced the production of N2O and increased the consumption of NH3.
Mi et al. [34] found that when NOx emission was reduced by diesel pilot
injection, the escape amount of NH3 was also reduced. And the emission
of NOx and the escape of NH3 were mitigated by Wang et al. [35]
through hydrogen blending in the cylinder.
A fundamental reduction in carbon emissions can be achieved by
increasing the substitution rate of ammonia and optimizing relevant
combustion parameters, which decreases the reliance on carbon-
containing fuels [33]. Whereas, the nitrogen contained in ammonia it­
self may result in the increase of NOx emissions. N2O is the typical ni­
trogen oxide which needs to be eliminated firstly. While NO still exhibits
Y. Qian et al.
an increasing trend at most ammonia/diesel mixed combustion condi­
tions. Therefore, the investigation of NOx sources is crucial in opti­
mizing ammonia/diesel in-cylinder combustion and mitigating
pollutant emissions. For example, in a model simulation study of
ammonia in-cylinder combustion, Lee et al. [36] categorized the NO
production process into four stages and emphasized that the thermal
type of NO production is primarily influenced by the peak temperature
within the cylinder. And the generation mechanism of NOx in ammonia-
fueled engine cylinders was investigated by Duan et al. [37] using a
detailed chemical mechanism. They identified two primary pathways,
NNH and N2O, for the fuel-based production of NOx. However, the
aforementioned studies about NOx formation sources were conducted
using small-bore high-speed diesel engines, and there are no relevant
researches available regarding large-bore marine engines. Furthermore,
the quantitative analysis of NOx sources in the in-cylinder ammonia/
diesel mixed combustion mode has not been carried out as well.
Considering the novel in-cylinder combustion environment, further
investigation is warranted to explore the sources of NOx generation in
detail.
In summary, the ammonia-doped in-cylinder combustion properties
in marine large-bore low-mid speed diesel engines are still unknown.
Although in-cylinder optimization studies have made progress in
reducing overall pollutant emissions in ammonia/diesel mode, meeting
regulatory requirements for NOx emissions remains great challenges.
Furthermore, quantitative analysis and comparison of NOx reaction
paths for in-cylinder ammonia/diesel mixed combustion mode were not
conducted, thus failing to provide substantial reference for reducing
NOx emissions in this mode. Therefore, in current study, a CFD model is
built based on bench test data of a marine diesel engine with a cylinder
diameter of 230 mm. The in-cylinder combustion and pollutant gener­
ation are performed under different combination strategies of ammonia
and diesel at three loads: 10 %, 50 %, and 100 %. At the same time, the
fuel injection timing (IT) are optimized simultaneously to enhance the
combustion efficiency of ammonia/diesel. In the calculation process, a
new coupling mechanism based on the simplified mechanism of n-
dodecane and ammonia is formed for the study of pollutant generation.
The coupling mechanism can reflect the formation process of different
types of NOx (thermal-NOx and fuel-NOx). Combined with the CFD
model, the thermal-NOx and fuel-NOx generated during the in-cylinder
cycle can be quantitatively analyzed. Also, the results of quantitative
analysis can provide reference for the further optimization direction of
in-cylinder combustion. And the research findings offer a valuable
theoretical basis for the further improvement of ammonia/diesel marine
engines.
2. Simulation setup and operating conditions
2.1. Engine geometry modeling
In current study, a full-scale three-dimensional combustion chamber
model is constructed based on the detailed parameters of the cylinder,
intake and exhaust ports in a 6-cylinder medium-speed marine diesel
Table 1
Main parameters of the engine.
Projects Parameters
Type Four-stroke
Cylinder bore/mm 230
Stroke/mm 320
Number of cylinders 6
Cylinder speed/(r⋅min-1) 900
Compression ratio 14.3
Intake valve opening moment / (◦ ) 55◦ BTDC
Intake valve closing moment / (◦ ) 35◦ ABDC
Exhaust valve opening moment / (◦ ) 55◦ BTDC
Exhaust valve closing moment/(◦ ) 45◦ ABDC
3
Fuel 360 (2024) 130617
engine (DE-23). The main parameters present medium-speed marine
diesel engine are shown in Table 1. The maximum supply pressure of
diesel fuel is 40 MPa.
Fig. 1 shows the schematic diagram of added ammonia injection
device in the prototype diesel engine. After the manifold injection, the
ammonia follows the gas motion and mixes with the in-cylinder air. The
3D computational fluid dynamics (CFD) model, which is based on the
relevant parameters within the cylinder of the target model, is depicted
in Fig. 2. In the simulation process, the fuel spray process is treated using
adaptive mesh refinement. The fuel nozzle is positioned at the center of
the combustion chamber’s cylinder head. The 12 injection holes are
uniformly distributed along the circumference. The angles among the
injection bundles are 140◦ .
2.2. Methods of simulation
In this simulation work, a commercial CFD code is used to simulate
the established dynamics mesh model. The mesh of the object model is
generated by the bounded model motion boundary. During the
computation of the execution code, adaptive mesh refinement (AMR) is
used to simulate the variation of relevant parameters including fluid
velocity and temperature during the operation of the cylinder. At the
same time, the mesh size is chosen as 1.5 mm to ensure the calculation
accuracy and efficiency. Fig. 3 illustrates the calculation results of mesh
irrelevance. The selected model calculation nodes are not larger than 1
500000.
In the process of simulation calculation, the boundary condition
setting parameters include: intake temperature,intake pressure, diesel
temperature,injection volume and injection duration, exhaust back
pressure, and combustion chamber temperature; under the condition of
engine load at 10–100 %. These parameters are constantly adjusted with
the engine load (0–100 %). For example, the intake pressure will be
adjusted according to the different load of the engine, as the engine load
increases, the intake pressure will correspondingly rise. The intake
pressure will be adjusted appropriately (±8 kPa) according to the intake
volume during the simulation. Ammonia is supplied through the nozzle
in the inlet. And the assumption is made that the mixture of ammonia
and air entering the cylinder is uniformly blended, aiming to enhance
calculation efficiency and reduce computation time. Meanwhile, the fuel
ratio is determined based on the cylinder filling material content when
the inlet is closed, aiming to minimize combustion process errors. The
fuel ratio under different conditions is described in detail in the
following simulated cases.
To improve computational efficiency, the relevant mature sub-model
code is coupled in the reaction kinetics CFD code, and the details of sub-
models are shown in Table 2. Meanwhile, to improve the accuracy of the
simulation results, the SAGE detailed chemical reaction kinetics solver is
used in the solving process.
SAGE, as a detailed chemical reaction kinetics solver, needs to be
coupled with a specific format of chemical reaction mechanism files in
order to operate effectively. In current study, ammonia and diesel are
used as the main fuel for in-cylinder combustion, making the original n-
heptane reaction mechanism paper no longer applicable to this simu­
lation process. Among them, diesel, as the main energy share fuel, also
plays an important role in igniting the ammonia component. A simpli­
fied reaction mechanism document of n-dodecane (54 species and 269
reactions), which is developed by Yao et al [38], is employed to analyze
the diesel combustion progress. This mechanism ensures the reaction
characteristics at high temperatures while improving the prediction
performance of ignition delay at low temperatures. While the Otomo
mechanism (32 species and 213 reactions) [39] is adopted for calcu­
lating ammonia combustion progress. The mechanism accurately pre­
dicts the laminar flame SPEED and ignition delay time across a wide
range of equivalent ratios and pressures, highlighting NH2, HNO, and
N2H2 reactions as pivotal mechanisms in the oxidation of ammonia in
this model. In the composite injection combustion process, the
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 1. The engine test bench diagram.

Fig. 2. The details of engine model.

combined chemical reaction mechanism based on the above two is used. Fig. 3. Mesh size independence verification.
The sensitivity analysis of various primitive reactions under wide
operation conditions are investigated as well. Through above analyses,
Table 2
the overlapping primitive reactions are deleted and the kinetic param­
Code coupling sub-model.
eters of important primitive reactions are modified to compose a finally
combined reaction mechanism containing 76 species and 460 steps of Physical process Model

primitive reactions. The calculation results presented by the combined Fuel injection Diesel Nozzle Flow
mechanism can accurately capture the key properties in reaction pro­ Droplet fragmentation KH-RT model
Droplet evaporation Dukowicz model
cess. It has also been verified and used in previous research work[40].
Turbulent flow k-epsilon
Fig. 4 shows the laminar flame velocity of n-dodecane-air mixture Fuel combustion SAGE
calculated based on the coupling mechanism, which verifies that the Generation of carbon smoke Hiroyasu-NSC
coupling mechanism can better present the combustion characteristics. Generation of nitrogen oxides Extending the Zeldovich model
And the relevant data in Fig. 4 are taken from the recent research lit­
eratures [41–44].
denoted as ‘N2*’. The elementary reactions related to the generation of
In the calculation process of pollutant generation, the calculation
thermal NOX in ‘mech.dat’ file is modified to avoid the influence of
model is adjusted to distinguish fuel generated NOx from thermal NOx.
thermal NOx on the calculation results. The data of ‘N2*’ in ‘therm.dat’
In regard to fuel NOX generation, ‘N2′ in the intake flow and cylinder are
and ‘gas.dat’ is consistent with N2, in order to mitigate any potential

4
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 4. Comparison of laminar flame speeds for different reaction mechanisms.

impact on the thermodynamic process within the cylinder and minimize

associated errors. Fig. 5. Ammonia gas supply based on engine load.

2.3. The cases of simulation
In this simulation research, the variation of in-cylinder combustion
characteristics with different ammonia energy ratios (AER) at different
engine load conditions is investigated. At the same time, the effect of the
variation pattern of the fuel supply parameters on the in-cylinder
mixture combustion characteristics is also the main content of this
study. And the details of simulation case are shown in Table 3. In the
selection of the simulated operating conditions, three power points of
10 %, 50 % and 100 % are selected. The marine engine operating speed
is constant at 900 rpm. Diesel and ammonia are supplied according to
the energy share. The relationship among ammonia supply, ammonia
energy ratio and engine load is shown in Fig. 5. Among them, the
amount of ammonia supplied per cycle ranges from 0.1g to 1.8g. The
amount of diesel supplied per cycle ranges from 0.28g to 1.56g; and the
parameter setting process involves making adjustments based on the
working conditions outlined in Table 3.
The research of the Reiter et al [29] shows that the flame combustion
is stable with the energy share of ammonia between 40 % and 60 %. And
Yousefi et al [45] studied the characteristics of ammonia-wood mixed
combustion under single operating conditions in this range. So based on
the above findings, the energy share of ammonia in this study was
selected as 5 %, 25 % and 45 %.
3. Results and discussion
3.1. Model validation
After establishing the computational model, the variation patterns of
the relevant state parameters during the in-cylinder combustion process
were calculated based on the set parameters of the diesel engine during
the experimental procedure. The degree of discrepancy between the
simulation results and the experimental measurements was used to
validate the computational accuracy and robustness of the constructed
three-dimensional computational model.
Fig. 6 illustrates the comparison between the maximum cylinder
pressure obtained from experimental measurements and that calculated

Table 3
The case of simulation set up.
Case Load Diesel fraction SODI Ammonia fraction
Ratio (%) (◦ BTDC) (%)

Case1- 10 %
1,2,3 95 %,75 %,55 % 6 5 %,25 %,45 %
Case1- 50 %
4,5,6
Case1- 100 %
7,8,9
Case2- 10 %
1,2,3 95 %,75 %,55 % 9 5 %,25 %,45 %
Case2- 50 %
4,5,6
Case2- 100 %
7,8,9
Case3- 10 %
1,2,3 95 %,75 %,55 % 11 5 %,25 %,45 %
Case3- 50 %
4,5,6
Case3- 100 %
Fig. 6. Comparison of simulated cylinder pressure and experimentally
7,8,9
collected cylinder pressure.

5
Y. Qian et al.
by the model. To mitigate measurement errors caused by value fluctu­
ations, the cylinder pressure data was collected three times under
identical working conditions during the experiment.
The data collected three times are represented by different colors in
figure. With the increase in engine load, the model output consistently
falls within the range of experimental measurements. The disparity be­
tween the model outcomes and experimental findings in terms of the
maximum cylinder pressure value ranges from 2 % to 5 %. It shows that
the simulation model demonstrates a high level of accuracy in predicting
the dynamic changes in cylinder pressure.
The combustion efficiency and energy conversion process in the
cylinder can be further characterized by comparing the trend of exhaust
temperature changes. The comparison between the exhaust temperature
predicted by the model and the exhaust temperature measured by the
experiment under 10–100 % load of the engine is illustrated in Fig. 7.
Due to the potential for measurement errors caused by the method and
tool utilized, the exhaust temperatures are observed have a range during
experimentation under varying loads. It can be seen from the figure that
under different loads, the predicted exhaust temperature of the model is
within the error range of the experimental measurement. The results
demonstrate that the model exhibits a high level of accuracy in pre­
dicting energy conversion processes and simulating combustion effi­
ciency, thus rendering it suitable for further research in simulation.
3.2. Influence of ammonia/diesel ratio on in-cylinder combustion
Based on previous optimization results of injection parameters under
pure diesel fuel conditions of current marine engine [46], the injection
timing of diesel fuel was selected as 9◦ BTDC at different ratios of
ammonia and diesel fuel mixtures. The simulation results of the pure
diesel fuel condition are compared with that of ammonia/diesel mixed
fuel conditions.
Fig. 8 illustrates the changes in cylinder pressure and heat release
rate with crankshaft angle under three engine loads of 10 %, 50 %, and
100 %. The cylinder pressure slightly increases as the proportion of
ammonia energy increases under 10 % low-load engine condition; at
AER = 45 %, the in-cylinder pressure rise near top dead center reaches
approximately 3.5 %, and there is a delayed trend in the CA corre­
sponding to the maximum pressure. Based on the variation trends of
heat release rate, as the AER increases, the peak phase of heat release
rate also advances. The reason may be that diesel injection amount is
small under light load conditions. As the ammonia ratio increases, there
is an increase in gaseous fuel within the cylinder, resulting in a
Fig. 7. Comparison of simulated exhaust temperature and experimentally
collected exhaust temperature.
6
Fuel 360 (2024) 130617
shortened fuel evaporation process and a relatively accelerated com­
bustion rate. Consequently, the peak phase of heat release rate advances,
and the step point of the pressure in the cylinder near the peak phase of
heat release also tends to advance.
When the engine is subjected to medium and high loads, there is a
tendency for the peak pressure in the cylinder to decrease as the AER
increases. Moreover, an increase in AER value leads to a greater
reduction in peak pressure. However, the variation law of heat release
rate remains unchanged. As the NH3 energy proportion increases, there
is an observed increase in the peak value of heat release and a corre­
sponding advancement in the phase. This indicates that under medium
and high loads, the initial phase of the in-cylinder combustion process
may be predominantly characterized by a mixed combustion of gases,
resulting in an accelerated rate of combustion [47]; and the phase of
heat release rate advances with the increase of ammonia energy ratio,
which is also found in the test results of Yousefi et al. [45].
It should be noted that the variation in in-cylinder pressure with AER
at 10 % load exhibits an opposite trend compared with that observed
under 50 % and 100 % load conditions. At low load conditions, the total
in-cylinder released energy is relatively small. Thus the introduction of
gaseous fuel can alter the total specific heat capacity of in-cylinder gas,
which impacts the combustion heat release process [48]. Whereas, at
medium and high loads, the increasing released heat from fuel during
combustion process counteracts the influence of changes in total specific
heat capacity of in-cylinder mixture.
The maximum burst pressure in the engine cylinder during com­
bustion is closely correlated with both the efficiency and rate of com­
bustion within the cylinder. Fig. 9 shows the phase of the peak firing
pressure (PFP) changes with the ratio of ammonia energy under 10 %,
50 % and 100 % load conditions. Under the 10 % engine load condition,
as the AER increases from 0 % to 45 %, there is a consistent backward
phase shift observed in PFP, and the rate of this phase shift exhibits a
linear relationship with AER. Under 50 % engine load condition, the
phase of PFP remains relatively stable, with only a slight delay of
approximately 8.3 % observed under an AER condition of 45 %. When
the engine load reaches 100 %, there is a backward delay observed in the
phase of PFP at an AER of 5 %. However, with an increase in AER to 45
%, a slight tendency for the phase of PFP to advance becomes evident.
The phase change of PFP may be closely correlated with the temperature
and pressure of combustion in the cylinder; in the in-cylinder combus­
tion stage, the combustion of liquid fuel undergoes a series of steps
including injection, evaporation, mixing, and combustion[30], and the
premixed gaseous fuel within the model can directly partake in the
combustion process. Therefore, during the low load stage, the temper­
ature and pressure in proximity to top dead center (TDC) are relatively
subdued, thereby facilitating a more discernible manifestation of
gaseous fuel combustion characteristics; and the combustion rate of
ammonia is lower than that of alkanes [39], resulting in a significant
backward delay in the phase of PFP. Under medium and high load
conditions, the temperature and pressure in the cylinder rise, leading to
an acceleration in combustion speed. Consequently, the distinct com­
bustion characteristics of gaseous fuel become less prominent. Com­
bined with the advanced phenomenon of heat release rate shown in
Fig. 8, it can be observed that the increase of AER has minimal impact on
the phase of PFP under both 50 % and 100 % engine load. Moreover, the
relationship between PFP phase and engine load remains consistent
across various AER working conditions, indicating that higher engine
loads correspond to earlier PFP phases. So the combustion characteris­
tics of ammonia/diesel mixture may be the underlying factor, resulting
in a more concentrated main combustion period around TDC. A detailed
analysis of the specific phase change law during combustion will be
conducted subsequently.
The critical stages of the combustion process are denoted by CA10,
CA50 and CA90, which respectively correspond to the crankshaft angle
positions at which 10 %, 50 % and 90 % of heat is accumulated during
the combustion cycle. Fig. 10 (a), (b) and (c) depict the in-cylinder
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 8. The variation of cylinder pressure and heat release rate with ammonia ratio.

combustion phase variation with respect to the ratio of ammonia energy

Fig. 9. Variation of the phase of PFP (Peak Firing Pressure) with different
ammonia energy ratio.
at engine loads of 10 %, 50 % and 100 %, respectively. Among them, the
value of CA50 represents the crankshaft Angle rotated by SOI-CA50. The
initiation of combustion is typically defined as the angular displacement
of the crankshaft from the start of injection commencement (SOI) to
CA10. The figure illustrates that the increase in AER under 10 % load
condition has negligible impact on SOI-CA10 value and ignition nucleus
formation process remains largely unchanged. However, under 50 %
and 100 % engine load, the value of SOI-CA10 decreases with increasing
AER. Among them, the nucleation time is reduced by 61.5 % at under 50
% load, while the formation time of fire nucleus is decreased by 46.6 %
at 100 % load. The formation time of the fire core is significantly
reduced under medium and high engine loads, leading to improved
combustion stability and flame quality. The reason of this change can be
attributed to the elevated temperature and pressure within the cylinder
during medium and high load conditions, which accelerates fuel com­
bustion. Secondly, the increase in the proportion of gaseous fuel resulted
in a reduction of mixing time and degree between the fuel and oxidizer,
thereby further expediting the initiation of combustion within the cyl­
inder. Additionally, the decomposition of free radicals by gaseous
ammonia in the cylinder under high temperature and pressure is also a
crucial factor in accelerating the formation of fire nuclei [49].
The early combustion timing is defined as the crankshaft angle be­
tween CA10 and CA50, which serves as a metric for assessing the effi­
ciency of combustion. In Figures (a) to (c), the crankshaft angle
corresponding to CA10-CA50 decreases as AER increases. Additionally,

7
Y. Qian et al.
Fig. 10. Combustion duration in cylinder under different ammonia energy ratio.
the phase of CA50 advances with increasing AER. In Figures (a) to (c),
the crankshaft angle corresponding to CA10-CA50 decreases as AER
increases. Among them, the phase of CA50 advances with increasing
AER. The reason may be that as the AER increases, the proportion of
premixed gas in terms of energy content also increases. This leads to a
more uniformly mixed premixed gas, which accelerates the develop­
ment of the flame surface and gradually brings the CA50 phase closer to
TDC. The same rule was also observed by Zhu et al.[47] in their simu­
lation calculation of ship engines with large cylinder diameters.
Furthermore, the decrease in the proportion of liquid fuel also resulted
in an accelerated combustion rate of the initial flame.
The crankshaft angle between CA10 and CA90 is commonly referred
to as the combustion duration, which directly impacts the thermal ef­
ficiency of the engine. The figure (a) illustrates that CA10-CA90 exhibits
a tendency of shortening with the increase of AER under the 10 % load;
when AER equals to 45 %, the combustion duration is reduced by 15–20
%. And the total combustion duration remains relatively unchanged in
figure (b) - (c). The observed phenomenon can be attributed to the
incipient stage of combustion at a load condition below 10 %, where the
fuel–air mixture plays a more significant role in the combustion process.
Subsequent to CA50, the accelerated burning rate of fuel vapor has
minimal impact on the overall duration of combustion. Consequently, it
is evident that the total combustion period (CA10-CA90) is predomi­
nantly influenced by the preceding stages of combustion before CA50,
rendering it highly sensitive to AER under low load conditions.
To gain a deeper understanding of the combustion process within the
8
Fuel 360 (2024) 130617
cylinder, an analysis is conducted on the temperature distribution under
100 % load conditions with IT = 9◦ BTDC. As shown in Fig. 11, the
highest temperature, average temperature and the distribution ratio of
in-cylinder charge with temperature > 2500 K are shown. And the
temperature variation trend was compared under different AER condi­
tions; by incorporating the temperature distribution in the cloud image,
an analysis of the combustion situation in the cylinder was conducted.
The Mean-temperature curve in the figure reveals a negative correlation
between the temperature in the cylinder and the increase of AER; based
on the cylinder pressure change shown in Fig. 8, it can be observed that
the inclusion of ammonia gas may enhance the specific heat capacity of
the cylinder charge and mitigate peak pressure and temperature near
TDC. The temperature distribution depicted in the cloud image also
verifies that ammonia gas within the cylinder diminishes high-
temperature regions adjacent to TDC. Under the condition of AER =
45 %, the temperature in the cylinder decreases more rapidly during the
later stages of combustion. This may be attributed to a decrease in
specific heat capacity of the cylinder charge after a significant amount of
ammonia gas has been consumed, resulting in an increased sensitivity to
changes in temperature. And it can be observed in figure of Mass Frac­
tion > 2500 K, when the AER reaches 45 %, there is a forward shift in the
peak point of the curve and a corresponding decrease in its area. This
results indicate a reduction in the high temperature region within the
cylinder, thereby validating the alteration rules of average temperature
under this operational condition. In addition, there is no significant
difference in Max-temperature variation in the figure. Combined with
Y. Qian et al.
Fig. 11. Temperature distribution during combustion in cylinder at 100% engine load.
the distribution proportion of high temperature charge, it can be seen
that the peak temperature may occur in regions around 0◦ CA.
3.3. Effect of injection timings on in-cylinder combustion of ammonia/
diesel mixture
The optimization of injection timing can significantly enhance the
combustion process of large bore diesel engines. In order to meet the
upgrading requirements and optimize medium-speed marine diesel en­
gines, considering the high economic and time costs associated with test
optimization, this section investigates the impact of diesel injection
timing on the combustion process under different load conditions
through model simulation. The specific conditions are presented in
Table 3.
The variation of engine cylinder pressure with diesel injection timing
is illustrated in Fig. 12, depicting conditions of AER at 5 %, 25 %, and 45
%. By comparing the variation trend of cylinder pressure in figure (a) -
(c), when calculating the in-cylinder pressure at 50 % and 100 % engine
load, variations in injection timing have minimal impact on the resulting
pressure; in close proximity to TDC, the maximum cylinder pressure at
IT = 11◦ BTDC exhibits less than a 5 % deviation from that observed at
IT = 6◦ BTDC. Maybe the temperature and pressure in the cylinder in­
crease under medium and high loads, potentially leading to enhanced
susceptibility of the charge in the cylinder to spontaneous combustion
due to the presence of gaseous fuel. However, the impact of injection
timing is clearly evident at 10 % engine load; it can be observed in the
figure that an increasing trend in the peak pressure value within the
cylinder as the injection timing advances. Additionally, through
comparing the difference of peak cylinder pressure in figure (a) - (c), a
higher AER leads to a greater disparity in pressure peaks under different
injection timing conditions. The peak pressure in the cylinder increases
by 10 % under the working condition of AER = 45 %, IT = 11◦ BTDC; this
can be attributed to a longer fuel evaporation period and a more
9
Fuel 360 (2024) 130617
concentrated combustion process near the TDC. Increasing AER im­
proves the in-cylinder premixing effect. Once the premixed gas is uni­
formly mixed within the cylinder, it enhances diesel igniting ammonia
effect and further boosts combustion efficiency [50]. The impact of in­
jection timing on the specific combustion process within the cylinder
can be further scrutinized below.
In order to gain a deeper understanding of the specific impact of
injection timing on in-cylinder combustion, Fig. 13 illustrates the vari­
ation pattern of combustion phase with injection timing under different
engine loads with AER = 45 %. Among them, the corresponding phase of
PFP under different working conditions has been marked in the figure
above. With the injection timing adjusted from 6◦ BTDC to 11◦ BTDC
under 10 % engine load, the overall combustion period advances, and
CA50 phase approaches TDC. However, the phase of PFP tends to be
delayed from 4.07◦ CA to 5.29◦ CA. This phenomenon indicates that
premature injection of diesel into the cylinder can result in excessive
heat absorption during evaporation [51], leading to a reduction in
combustion rate and a retrograde phase of PFP under low load condi­
tions. With an injection timing advance at 50 % load, the phase of PFP
advances and approaches TDC, indicating that in-cylinder combustion is
promoted and combustion efficiency near TDC is improved under this
condition. Under 100 % load, the variation trend of PFP phase remains
consistent with that observed under 50 % load and is closer to TDC.
However, injection timing has minimal impact on CA50 variation
amplitude. At the same time, the phase of CA10 experiences a delay after
TDC while the FPF phase advances. This indicates that the combustion
efficiency of an ammonia/diesel mixture could potentially be enhanced
under conditions of high temperature and pressure, consequently lead­
ing to an increase in the combustion rate [29]. During the downward
stroke of the piston, a rapid decline in temperature and pressure occurs,
resulting in a reduction in the combustion rate. As a result, there is an
amplified disparity between the combustion rates near CA10, which
subsequently leads to a narrower range of variation for CA50 and an
Y. Qian et al.
Fig. 12. The variation of cylinder pressure with different ammonia energy ratio and engine load.
advancement of the PFP phase. Therefore, further investigation is
required to optimize the fuel injection timing in conjunction with spe­
cific operating conditions for ammonia/diesel mixed combustion mode.
Fig. 14 shows the influence of different diesel injection timing on the
temperature distribution during in-cylinder combustion under 10 %
load, and the cloud image depicts the formation process of the SOI-CA10
fire nucleus. As depicted in the figure, when the diesel injection timing is
advanced to 11◦ BTDC, there is an approximately 10 % increase in
average cylinder temperature and a tendency for peak temperature
phase shift towards retardation. Additionally, the charge ratio of tem­
perature > 2000 K also increased by 2.6 times; however, there is only
minimal alteration in maximum cylinder temperature amplitude. The
results indicate that advancing the injection timing enhances combus­
tion within the cylinder under these conditions. This may be attributed
to a longer fuel mixing time, which allows for more evenly mixed diesel
components ignite more ammonia. Additionally, an increase in the ratio
of high temperature charge provides further support for this explana­
tion. It can be observed from the cloud image that with the advance of
the injection timing, the area of fire core formation in the cylinder is
relatively larger, and the proportion of high temperature area in the fire
core is also significantly increased. The results demonstrate that
advancing the injection timing can effectively enhance the combustion
efficiency of ammonia/diesel mixture under 10% load. However, the
10
Fuel 360 (2024) 130617
initial combustion involves a greater amount of ammonia, resulting in a
lower flame combustion rate and causing the PFP phase to shift back­
ward in Fig. 13(a).
Fig. 15 shows the variation law of temperature distribution in cyl­
inder with injection timing under 50 % load. Compared to 10 % load, the
average temperature in the graph exhibits less sensitivity to variations in
injection timing, resulting in smaller changes in both temperature peak
amplitude and phase. Through the curve of charge temperature > 2500
K, the high temperature area still increases when IT of diesel is
advanced; and this increase occurs in two distinct steps. When the IT =
6◦ BTDC, the peak value near TDC higher that near 18◦ CA, and the gap
between these peaks diminishes as the IT advances. At IT = 11◦ BTDC,
the second peak already exceeds the first. The reason may be that up­
ward piston compression and diesel combustion form the high temper­
ature area near TDC, and the second high temperature area is formed by
the combined action of ignited ammonia gas and evaporated fuel steam
combustion. Therefore, as the IT advances, the fuel evaporation time
increases and the diffusion area expands, leading to ignition of premixed
gas in multiple areas and a gradual increase in the proportion of the
second high temperature zone. Meanwhile, through the evolution of the
fire core in the cloud image, the development of high temperature flame
surface is relatively broad after advancing IT.
Based on the temperature distribution curve observed in Fig. 16, it
Y. Qian et al.
Fig. 13. Combustion duration in cylinder under different injection timing at AER = 45 %.
can be noted that IT has negligible impact on the average cylinder
temperature. However, in the curve of mass fraction, the area of the
second peak value at 6◦ BTDC is larger than that of the first peak value.
And with the advance of injection timing, the growth trend of the second
peak area is much larger than that in Fig. 15. The phenomenon can be
attributed to the fact that, under 100 % load, the temperature and
pressure within the cylinder are further elevated, leading to an accel­
eration in premixed gas combustion speed and an increase in flame
propagation area. Combined with the fire core development process in
the cloud image, it can be seen that the development areas of the fire
core flame surface at different IT are almost the same, so the difference
degree are small in the curve of the average temperature distribution in
the cylinder. Notably, when comparing the temperature distribution
cloud image at 10 % and 50 % loads, it is evident that there is a lesser
extent of development in the high-temperature region during the pro­
gression of the flame kernel. Furthermore, as the engine load increases,
there is a decrease in the peak value of the average in-cylinder tem­
perature. Combined with the temperature distribution cloud map in
Fig. 17, it is evident that as the load increases from 10 % to 100 %, there
is a noticeable reduction in the high-temperature region at TDC point
within the cylinder. The reason may be that the participation of
ammonia in combustion leads to a deceleration of combustion rate in
cylinder.
The combustion phase depicted in Fig. 10 reveals that CA10 prolongs
as the load increases. At 100 % load, the top dead center remains in the
stage of fire nucleus formation. Therefore, the slower rate of combustion
11
Fuel 360 (2024) 130617
and the influence of the piston downward after TDC result in a decrease
in the peak of the average temperature in the cylinder. Secondly, the fuel
injection duration may be extended after the engine load is increased,
the fuel injection duration of 10 % load has ended before TDC, and the
fuel injection duration of 50 % and 100 % load continues after TDC. As
can be observed in Fig. 17, the temperature near the TDC decreases
inversely with increasing load. The interaction between fuel spray and
wall surface further reduces the peak temperature at TDC [52]. There­
fore, advancing the injection timing can increase the peak value of
average cylinder temperature; however, this effect diminishes as engine
load increases and injection duration lengthens.
3.4. Effect of ammonia/diesel combustion on in-cylinder pollutant
generation
Fig. 18 shows the variation law of pollutant generation in engine
cylinder under 10 % (a), 50 % (b) and 100 % (c) engine load. The major
pollutants comprise nitrogen oxides (NOx), hydrocarbons (HC), and
carbon monoxide (CO). Under a 10 % engine load, the increase in AER
from 0 % to 25 % does not have a significant impact on both the quantity
and trend of NOx generation. However, when AER reaches 45 %, there is
a notable increase of 30 % in the amount of NOx generated. Perhaps, a
portion of NOx is converted by NH3 within the cylinder. The generation
of HC decreased as the AER increased, and at AER = 45 %, the HC
generation was 44 % lower compared to that at AER = 0 %. This in­
dicates that an increase in the proportion of ammonia energy within the
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 14. Distribution of temperature with different injection timing at AER = 45 %, load = 10 %.

Fig. 15. Distribution of temperature with different injection timing at AER = 45 %, load = 50 %.

cylinder can lead to a significant reduction in engine carbon emissions. 45 %, the generation rate of CO reaches its maximum, accompanied by
CO is intermediate product of in-cylinder combustion, and the variation the highest decline rate during the later stages of combustion. It is
of AER has minimal impact on its formation process. However, at AER = possible that CO has a strong reducibility, and REDOX reaction occurs

12
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 16. Distribution of temperature with different injection timing at AER = 45 %, load = 100 %.

Fig. 17. Distribution of temperature with different engine load at AER = 45 %, IT = 9◦ BTDC.

after a large amount of NOx generated in the cylinder [53,54], so there is
a tendency for decline in CO generation.
In 50 % and 100 % load conditions, the variation trend of pollutant
generation is similar, the difference between the variation amplitude of
the generated quantity in 100 % load is greater. The amount of NOx
generation decreases with the increase of AER. At the front of the
combustion period, the NOx generation rate is faster at AER = 45 %. It is
possible that the decrease of peak temperature and pressure in the cyl­
inder reduces the generation of thermal NOX after AER is raised;
although the generation rate of fuel-type NOX is faster, the generated
amount is relatively small. Secondly, the production of HC decreases as
AER increases, and the formation laws are same with that in 10 % engine
load. Finally, CO production decreases with the increase of AER. For this
phenomenon, on one hand, the reduction in the proportion of carbon-
containing fuel may result in CO emissions decreases. On the other
hand, the increase of gaseous fuel ratio makes the cylinder charge mix
more evenly, leading to enhanced combustion efficiency and reduced
CO generation. It should be noted that at AER = 5 %, the CO generation
is slightly higher than that with pure fuel condition, which may be
attributed to a small amount of NH3 in the cylinder impeding CO further
oxidation.
The ratio of NO2 to NO in the NOx components directly impacts the
proportion of rapid SCR, standard SCR and NO2 SCR reactions during
the SCR process, thereby influencing overall reaction efficiency[55].
Therefore, Fig. 19 illustrates the variations in the NO2 and NO pro­
portions within the cylinder under different AER. This analysis aims to
enhance our comprehension of the catalytic reaction potential of engine
exhaust in the ammonia/diesel dual fuel mode. As can be seen from the

13
Y. Qian et al.
Fig. 18. Formation of pollutants in cylinder with different AER at IT = 9◦ BTDC, load = 10 %,50 % and 100 %.
Fig. 19. Variation trend of NO2/NO in NOx components with different AER at
IT = 9◦ BTDC, load = 50 %.
figure, when ammonia gas participates in cylinder combustion, the
proportion of NO2/NO increases rapidly and then decreases, but the
amplitude of proportion change decreases with the increase of AER, and
the peak phase of the curve advances with the increase of AER. Indeed,
the higher temperature and pressure near Top Dead Center (TDC) can
significantly influence the reactivity of substances involved in combus­
tion. This is because the temperature and pressure near TDC are higher
and the reactivity of the substance is higher. When the proportion of
gaseous fuel in the cylinder increases, there will be a greater abundance
of free radicals with potent oxidizing capabilities during combustion. So
the proportion of NO2 in NOx will rise. In addition, the reducibility of
14
Fuel 360 (2024) 130617
CO and HC in the cylinder is strong, and reacted with NO2 causes the
decrease of NO2/NO ratio; residual NH3 within the cylinder can also
partially reduce NOx [56], resulting in a further decrease in the NO2/NO
ratio. Furthermore, based on the research findings of Supriyanto et al
[57], optimizing NO2/NO control within the range of 10–25 % can
effectively enhance the catalytic efficiency of SCR. It can be seen from
figure, the NO2/NO in the cylinder is maintained between 10 % and 25
% at AER > 5 %, so the NOx aftertreatment system in ammonia/diesel
dual fuel mode is more feasible to develop.
Fig. 20 presents NO generating sources in the cylinder under the
working conditions of 5 %, 25 % and 45 % AER. The sources of NO are
primarily categorized as Thermal NO and Fuel NO. Thermal NO is pre­
dominantly formed by the reaction between N2 and O2 in the high
temperature and pressure environment within the cylinder [58], while
fuel NO mainly originates from ammonia combustion within the cylin­
der [36]. It can be observed from the Fig. 21 that as AER increases from
5 % to 45 %, the proportion of Fuel NO increased from 75.5 % to 91.4 %.
Probably due to the three main reaction paths of NH3: NH3＞NH2＞NH
＞HNO＞NO, NH3＞NH2＞H2NO＞HNO＞NO, H2NO＞HNOH＞HNO
＞NO will all point to NO. The concentration of NH3 in the cylinder
increases, there are more NO source paths, and consequently causing a
continuous rise in the proportion of Fuel NO.
Secondly, the high temperature and pressure environment is inher­
ently unstable during the combustion process near TDC, so the genera­
tion of Themral NO is limited. Therefore, the conversion of NH3
becomes the main source of NO. It can be seen from Fig. 21 that with
AER increases, the proportion of NO decreases, and the proportion of
nitrogen oxides formed by N atoms of other chemical valence states
increases from 5.1 % to 8.1 %. This means a significant amount of ni­
trogen oxides are generated through the side reaction pathway of
ammonia, and as the proportion of NH3 in the cylinder increases, the
NOx composition becomes more complex. In summary, Fuel NO is the
primary contributor to NOx emissions in ammonia/diesel combustion
mode, and enhancing the combustion efficiency of ammonia can solve
the emission problem of NOx fundamentally.
Y. Qian et al. Fuel 360 (2024) 130617

Fig. 20. Source analysis of NOx during ammonia/diesel combustion in cylinder at IT = 9◦ BTDC, load = 50 %.

Fig. 21. The proportion of different types of nitrogen oxides at IT = 9◦ BTDC, load = 50 %.

15
Y. Qian et al.
4. Conclusion
In this study, a theoretical analysis of in-cylinder combustion was
conducted utilizing CFD simulation coupled with the reaction mecha­
nism of n-dodecane/ammonia. The reliability and calculation accuracy
of in-cylinder 3D model for a medium-speed marine diesel engine had
been validated through bench test data. The in-cylinder combustion
performance, the formation mechanism of pollutants, especially the
composition and source of NOx, under wide operation conditions
(including the ammonia energy ratios of 5 %, 25 % and 45 %, the engine
loads of 10 %, 50 %, and 100 %, the injection timing of 6, 9 and
11◦ BTDC) were compared and analyzed. Furthermore, the potential for
SCR reaction in exhaust gas was investigated as well. The main con­
clusions were summarized as follows:
1. In the ammonia/diesel dual-fuel combustion mode, as AER increases,
there was a corresponding increase in the gas fuel content within the
cylinder. This led to a shortened fuel evaporation process and an
accelerated combustion rate, advancing the phase of peak HRR. In
the first stage of combustion in the cylinder, premixed gas was the
main fuel, resulting in a small heat release and slow flame speed. And
the addition of ammonia alters the specific heat capacity of the gas in
the cylinder, leading to an increase in cylinder pressure as AER in­
creases at 10 % engine load. At 50 % and 100 % engine load, the
cylinder pressure decreased with the increase of AER. In terms of the
in-cylinder combustion phase, the sensitivity of CA10-CA90 to AER
gradually decreases with increase of load, indicating that engine load
and AER settings should be considered comprehensively.
2. The advance of injection timing prolongs the evaporation time of
diesel fuel, which improved the uniformity of diesel/premixed-gas.
Therefore, the combustion efficiency and in-cylinder peak pressure
were increased. As AER increases, the premixing effect is enhanced,
and the area where diesel igniting ammonia increases. The devel­
opment of flame surface in the combustion chamber also indicated
that advancing injection timing accelerated flame propagation and
expanded the high-temperature region. And advancing injection
timing also improved the combustion efficiency in the second stage
of the diesel/ammonia combustion process. Further, when AER = 45
%, the peak value of in-cylinder average temperature was reduced
due to the interaction between spray and wall under medium and
high loads. Therefore, the application potential of the ammonia/
diesel mixed combustion mode merits further investigation.
3. The involvement of ammonia in the combustion process can effec­
tively mitigate the emissions of unburned hydrocarbons (HC) and
carbon monoxide (CO). The reduction of NOX emissions could be
effectively achieved at medium and high engine loads. With the rise
in AER, there was more pronounced positive impact on reducing
pollutant emissions. Under ammonia/diesel mixed combustion
mode, the NO2/NO ratio in NOx emissions fell between 10 % and 25
%, which was within the high-efficiency concentration range of re­
actants for SCR. This significantly reduces the complexity of devel­
oping SCR system.
4. With the increase of AER, that leads to a reduction in the proportion
of high temperature area within the cylinder, and the generation of
Thermal NOx decreases; the majority of NOX in the cylinder are Fuel
NOX. Therefore, the emission of nitrogen oxide (NOx) poses a sig­
nificant challenge in ammonia/diesel mixed combustion mode. And
optimizing combustion process of NH3/diesel can reduce the gen­
eration of NOX from the source.
Future expectations:
The aforementioned research demonstrates that ammonia exhibits a
wide range of potential applications in compression ignition (CI) en­
gines. Combined with its relatively mature industrial chain, ammonia
has a strong competitiveness in economy and environmental protection
in the field of marine medium and low speed large cylinder diameter
16
Fuel 360 (2024) 130617
engines. The future research direction encompasses investigating liquid
ammonia direct injection combustion in cylinder, exploring low tem­
perature combustion modes based on ammonia fuel, and developing
exhaust gas purification systems for ammonia engines.
CRediT authorship contribution statement
Yejian Qian: . Yu Sun: Writing – original draft, Methodology,
Formal analysis, Data curation. Zhen Gong: Writing – review & editing.
Shun Meng: Formal analysis. Xiaofei Wei: Software. Binbin Tang:
Resources. Juye Wan: .
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
Data will be made available on request.
Acknowledgments
The work in this study received financial support from Science and
Technology Major Project of Anhui (China) (Grant
No.202003a05020023), National Natural Science Foundation of China
(No. 51676062), Fundamental Research Funds for the Central Univer­
sities (Grant No. JZ2023HGQA0139).
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