Journal of Cleaner Production 450 (2024) 141959

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Study on ammonia/methanol blends with ammonia cracking for

low-carbon combustion and NO reduction
Xiangyu Meng a, *, Lizi Liu a, Meichao Qin a, Menglan Miao a, Hang Zhao a, Wuqiang Long b,
Mingshu Bi a
a
School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning, 116024, China
b
Institute of Internal Combustion Engine, Dalian University of Technology, Dalian, Liaoning, 116024, China

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

Handling Editor: Panos Seferlis This work aims to study the ammonia/methanol blended fuel with ammonia cracking in lean-burn condition.
Ammonia on-line cracking to produce hydrogen production has the potential to realize the high-efficiency
Keywords: combustion. A new ammonia/methanol/hydrogen mechanism was updated and simplified using several
Ammonia/methanol reduction methods to optimize the computation time in 3D simulation. Visualization measurements in constant
Ammonia cracking
volume combustion chamber (CVCC) for flame propagation and NO generation were conducted, and 3D
Visualization measurements
computational fluid dynamics (CFD) modeling was also established with the simplified mechanism simulta­
Chemical kinetics
3D modeling neously to investigate the impact of methanol addition and ammonia cracking in the lean-burn mode. The
findings showed that methanol addition and ammonia cracking can significantly improve the combustion rate,
and 60%ammonia/40%methanol with ammonia cracking ratio of 90% (N60R90) at equivalence ratio (ER) of 0.7
yields the similar LBV as pure methanol at ER of 1.0 in laminar burning condition. Its ER can be extended to 0.4
to obtain the similar level of LBV as pure ammonia at 1.0. The experiments and 3D simulations revealed that
N60R90 at 0.4 yields the equivalent level of combustion rate as N60R0 at 0.8, while obtaining much lower NO
emission. In addition, N60R100 at 0.4 without fuel-NO formation during the combustion can get ultra-low NO
emission. This study provides the insights on low-carbon combustion strategy for ammonia cracking with low
NO.

1. Introduction
The utilization of fossil fuels has greatly increased the labor pro­
ductivity and allowed for rapid economic development while bringing
about the global warming problem. Currently, the use of clean alter­
native fuels to reduce carbon emissions has become one of main con­
cerns. Ammonia fuel can participate in the process of combustion to
provide energy without carbon emission generation, whose combustion
process has received wide attention (Cardoso et al., 2021; Feng et al.,
2023; Meng et al., 2023c).
Ammonia not only produces CO2-free emissions during combustion,
but it also proves to be more cost-effective, efficient, and safer in terms
of storage and transportation. Utilizing ammonia-containing fuel has
emerged as an effective approach to control carbon emissions and
achieving carbon peaking targets (Cai et al., 2023). However, ammo­
nia’s widespread application in engines faces certain challenges (Lu
et al., 2023). Its slow combustion rate characterized by a significantly
lower laminar burning velocity (LBV) compared to hydrogen, along with
its lower mass calorific value, higher ignition energy requirements, and
high NOx emissions (Frigo and Gentili, 2013), limit its application in
engines (Meng et al., 2023b). To address these issues, several studies
have been conducted by the scholars, exploring the promotion of
ammonia ignition and oxidation by using auxiliary fuels to reduce the
pollutants. These fuels comprise Hydrogen (H2), Methane (CH4), alco­
hols, diesel, Dimethyl Ether (DME) and n-heptane, etc (He et al., 2022;
Liu, L. et al., 2022a; Meng et al., 2024b; Meng et al., 2022; Wang et al.,
2021; Wen et al., 2023).
Methanol is the simplest saturated mono-alcohol, and it is considered

Abbreviations: 1D, One Dimension; 3D, Three-Dimension; CFD, Computational fluid dynamics; AMR, Adaptive mesh refinement; CVCC, Constant Volume
Combustion Chamber; DRGEP, Directed Relation Graph with Error Propagation; DRGEPSA, Directed Relation Graph with a Sensitivity Analysis; ER, Equivalence
Ratio; IDT, Ignition Delay Time; LBV, Laminar Burning Velocity; QSS, Quasi-steady State; RCM, Rapid Compression Machine.
* Corresponding author.
E-mail address: mengxiangyu@dlut.edu.cn (X. Meng).

https://doi.org/10.1016/j.jclepro.2024.141959
Received 5 November 2023; Received in revised form 27 February 2024; Accepted 25 March 2024
Available online 27 March 2024
0959-6526/© 2024 Published by Elsevier Ltd.
X. Meng et al. Journal of Cleaner Production 450 (2024) 141959

as one of the most favorable alternative fuels for engine application,

resulted from its high oxygen content, high octane number, wide sources
and abundant reserves (Gong et al., 2019; Maimaiti et al., 2023). In an
experimental study conducted by Ariemma et al. (Ariemma et al., 2023;
Wei et al., 2023), it was found that ammonia/alcohol (including meth­
anol) blends can expand the region in which stable burning is attained
and have lower NOx emissions compared to ammonia/methane blends.
It also showed that ammonia/methanol blends have the potential to be
used in engines.
Wang et al. (2021) employed heat flux approach to test LBV of
NH3/CH3OH blended fuel under various operating conditions, including
different temperatures (298–448 K) and equivalence ratios (ERs), all at
1 atm pressure. They also investigated the reaction mechanism of this
blended fuel, and the kinetic study showed that the effect of adding
oxygenated alcohols in ammonia on LBV was similar to that of H2 or
CH4. Consequently, methanol addition leads to an increased combustion
rate of the blended fuel. Xu et al. (2022) studied the combustion be­
haviors of NH3/CH3OH blends and developed a simplified mechanism.
According to a reaction pathway analysis, it showed that the methyl
radical generated by the oxidation of methanol contributes to the
ammonia dehydrogenation process. The highest NOx emission was
found when the methanol percentage was 60%. Li et al. (2022) inves­
tigated the ignition delay time (IDT) of NH3/CH3OH with three ERs
Fig. 1. Flow chart of mechanism simplification.
using a rapid compression machine (RCM) at 2 and 4 MPa and tem­
peratures from 845 to 1100 K. The detailed ignition mechanism for
NH3/CH3OH was also established, which can better simulate the igni­ previously established NH3/CH3OH/H2 mechanism has been updated
tion transportation behavior. Li et al. (2023) studied the impact of and further simplified. The lean-burning condition of partial ammonia
methanol addition on the auto-ignition of ammonia and measured IDT cracking in ammonia/methanol blends were analyzed in laminar
of NH3/CH3OH blends under pressures from 0.14 to 1.0 MPa and tem­ burning condition. Flame propagation and NO chemiluminescence ex­
peratures of 1250–2150 K in a shock tube. A simplified mechanism was periments in a constant volume combustion chamber (CVCC) and 3D
developed as well. They found that by adding 5% methanol, the IDT of simulations were also performed for the engine conditions to investigate
NH3/CH3OH blends can be shortened by over a half. the lean burn operation with ammonia cracking.
Hydrogen, being cleaner than fossil fuels, also represents an ideal
carbon-free fuel for engines (Seelam et al., 2022). Utilizing thermal 2. Kinetic modeling and validations
cracking of ammonia to generate hydrogen presents a solution to over­
come the safety and cost challenges associated with conventional 2.1. Chemical reaction mechanism development and simplification
hydrogen storage technologies (Liu, W. et al., 2022b; Meng et al., 2023a;
Mercier et al., 2022). Ammonia cracking to produce H2 and N2 can occur A chemical reaction mechanism including NH3, H2, CH3OH and their
at temperatures up to 200 ◦ C (Lan et al., 2012). It is significantly affected blends was developed previously (Meng et al., 2024a), and
by temperature and catalyst, and the conversion efficiency can reach to sub-mechanisms of NH3, CH3OH and C–N were derived from Glarborg
98–99% at 700 K (Klerke et al., 2008), and the thermal cracking of et al. (2018), Liang et al. (2020) and Konnov mechanism (Konnov,
ammonia is occurred at elevated temperatures up to 775 K without 2009), respectively. The rate constants of partial reactions were updated
catalyst (Ma et al., 2006). In addition, the heat requirement for ammonia according to the references (Baulch et al., 2005; Gao et al., 2016; Li
cracking can be provided by the engine exhaust heat. Mei et al. (2021) et al., 2022) for the wide validations. Consequently, a reaction mecha­
investigated LBV for partially cracked ammonia/air mixture at 1 MPa, nism including 59 species and 344 reactions was developed. In order to
and the test results indicated that the cracking of ammonia can signifi­ shorten the calculation period in 3D computational fluid dynamics
cantly promote the flame propagation. The thermal effects generated by (CFD) numerical simulation, the mechanism was simplified firstly using
H2 and N2 after cracking were separated from other effects via the vir­ a couple of reduction methods. As shown in Fig. 1, the process of
tual dilution gas method, and it revealed that the chemical effect has the mechanism simplification in this study relies on the elimination of
greatest impact on flame development. Ji et al. (2022). measured LBV of redundant species and primitive reactions during combustion, and LBV,
blended fuels at different ratios of ammonia cracked gas. It showed that IDT, and NO are used as the target parameters for mechanism simplifi­
the peak LBV of the fuel mixture is increased up to 228 cm/s due to the cation with a maximum error criterion of 3%.
ammonia cracking. These studies showcase the potential of utilizing The directed relation graph with error propagation and sensitivity
ammonia cracking to generate hydrogen-rich gas, thereby enhancing the analysis (DRGEPSA) method was firstly applied, which is separated into
combustion of ammonia-containing fuels. In addition, the efficiency of two main stages. The first stage is the species deletion from the species
ammonia cracking depends on the temperature of the exhaust gas and analysis with the directed relation graph with error propagation
performance of the cracking catalyst, which affects the direct use of the (DRGEP), which considers the impact of error transfer in relational
cracked gas and the combustion process. However, partial cracking of graphs on the indirect coupling relationships of the components. The
ammonia can also provide hydrogen-rich gas to facilitate combustion. second stage is the sensitivity analysis (SA), which introduces a
According to previous literatures, it has been observed that adding customized sensitivity analysis threshold with 10− 5 based on the DRGEP
either hydrogen or methanol to ammonia fuel can effectively promote simplification. The removable specie error is calculated by comparing it
the flame propagation. Notably, hydrogen can be produced by ammonia with the threshold size. Seventeen species were finally removed using
cracking. It has greatly potential to be used in engines with these DRGEPSA, most of which were C–N components. Accordingly, a
blended fuels. However, the combustion and emission behavior, as well mechanism including 42 species and 283 reactions was obtained.
as the chemical reaction processes for ammonia/methanol with In the second step, the mechanism was further simplified using the
ammonia cracking, have not been thoroughly studied. In this work, the method of computational singular regression (CSP). The quasi-steady

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X. Meng et al.
Fig. 2. Comparison of experimental data and LBV calculation results with original and simplified mechanisms.
Fig. 3. Comparison of experimental data and IDT calculation results with original and simplified mechanisms.
state (QSS) species which have minimal contribution to the simulation
of combustion characteristics can be detected using CSP. After the
simplification of the DRGEP method, using CSP did not perform any
further species deletion, but 83 reactions mainly including N–H, C–O
interactions were removed based on the error criterion. Finally, a
simplified mechanism with 42 species and 200 reactions was obtained.
2.2. Mechanism validations
The mechanism was comprehensively validated via a broad range of
initial parameters, and the original and simplified mechanisms are
presented simultaneously for the comparisons in Figs. 2–4. Fig. 2 pre­
sents the LBV predictions of original and simplified mechanisms. NH3/
CH3OH, NH3/H2, and CH3OH/H2 for different blending ratios are
compared for the initial temperatures ranging from 298K to 448 K,
initial pressures ranging from 0.1 MPa to 0.7 MPa, and ERs ranging from
0.6 to 1.5, and it reveals that the predictions of mechanism coincide with
the experimental data (Ichikawa et al., 2015; Jin et al., 2022; Lee et al.,
2010; Li et al., 2017; Wang et al., 2021; Xiao et al., 2022) very well. As
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Journal of Cleaner Production 450 (2024) 141959
shown in Fig. 3, IDTs of NH3 and NH3/H2 were validated for 0.1–3 MPa
and 950–2500 K (Burke et al., 2016; Chen et al., 2021; He et al., 2019; Li
et al., 2022, 2023; Mathieu and Petersen, 2015; Pinzón et al., 2019).
IDTs of CH3OH and NH3/CH3OH were validated for 0.1–4 MPa and
850–1800 K. The comparisons reveal that the IDT predictions with this
mechanism for the blended fuels of NH3, CH3OH, and H2 are in good
agreement with the experimental data.
One of the prominent problems of ammonia-containing fuels is the
NOx emission, so this paper also conducts the validation of the NO
emission prediction with the mechanism as shown in Fig. 4. In addition,
when the ammonia is completely cracked, there is no fuel-NO during the
combustion, so the NO generation during the combustion of pure
methanol is also simulated as shown in Fig. 4b. It can be found that the
NO predictions for pure ammonia at 298 K and 0.3 MPa (Hayakawa
et al., 2021), pure methanol at 318 K and 0.1 MPa (Brackmann et al.,
2020) are favorable at different ERs below 1.0. It slightly underestimates
the NO generation for ER higher than 1.2 for methanol, while this work
refers to the lean-burn condition, so the prediction is acceptable. Be­
sides, the NO predictions for the NH3/H2 blended fuel (Osipova et al.,
X. Meng et al.
Fig. 4. Comparison of experimental data and calculated results of NO emissions with original and simplified mechanisms.
2021, 2022) are shown in Fig. 4c, and it also presents the acceptable
trend.
3. Experimental setup
The visualization measurements in this work were conducted in a
CVCC test system as shown in Fig. 5, and the pressure trace, flame
propagation and NO chemiluminescence were measured during the
combustion process. The test system mainly consisted of the main body
of the combustion chamber, gas control, ignition, high-speed schlieren
testing, NO chemiluminescence testing, heating, and data acquisition
systems. The experimental system was mainly divided into four systems,
including light path, gas path, control and heating system. The light path
system can be achieved through the light source and the slit to achieve
the adjustment of the brightness of the grain. In the gas path system,
ammonia, methanol, and hydrogen were transported through the pipe­
line directly into the combustion chamber to achieve premixing. The
control system, utilizing the CompactRIO platform, completed tasks
such as igniting the spark plugs, acquiring pressure and temperature
information, and conducting high-speed photography. The heating
system comprised heating rods and a temperature control cabinet used
to regulate the initial temperature. The pressure sensor had a sensitivity
of 14 pc/bar and a measuring range of 0–200 bar, while the temperature
sensor had an uncertainty of ±1 ◦ C and a measuring range of − 50 to
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Journal of Cleaner Production 450 (2024) 141959
1300 ◦ C. The camera was a C-MOS type with a frame rate of 20,000 fps,
an exposure time of 1/20409, a pixel count of 836 × 720 (width ×
height), and a resolution of 3.8 pixels/mm.
The experimental parameters are listed in Table 1. The experiments
with CH3OH/NH3 blended fuels were conducted at an ER of 0.9, 550 K,
and 1.3 MPa. The combustion process was measured for fuels with
methanol energy ratios of 20% and 40%, respectively. Experiments with
H2/CH3OH blends were conducted at an ER of 0.6, 500 K, and 1.0 MPa,
with a hydrogen energy ratio of 20%.
Ammonia, hydrogen, and methanol fuels were injected in controlled
amounts using the partial pressure method. During the experiment, a
specific amount of air was introduced into the combustion chamber
firstly. CH3OH/NH3 and H2/CH3OH were then sequentially introduced
according to the pressure, followed by the addition of air to restore the
pressure to its initial condition. The mixture was ignited by a spark plug
mounted in the upper part of CVCC. A high-speed camera, coupled with
a schlieren testing system, was used to measure flame propagation.
Additionally, an image intensifier with a specific wavelength lens was
employed to measure the chemiluminescence of NO. The pressure sensor
was utilized for pressure data acquisition in the combustion chamber.
4. 3D CFD modeling methodology
A CVCC model as used in the experiments was established, and the
X. Meng et al. Journal of Cleaner Production 450 (2024) 141959

Fig. 5. Schematic diagram of the experimental setup.

Table 1
Experimental parameters.
Initial Initial pressure/ Equivalence
temperature/K MPa ratio

20%CH3OH/80% 550 1.3 0.9

NH3
40%CH3OH/60% 550 1.3 0.9
NH3
20%H2/80% 500 1.0 0.6
CH3OH

combustion process of ammonia/methanol with ammonia cracking

under lean-burn condition was studied in Converge 3D CFD software.
The RNG k-ε model (Han and Reitz, 1995) was chosen to simulate the
turbulent flow during the combustion, and SAGE model embedded in
the simplified mechanism was applied to calculate the flame propaga­
tion process. Considering the non-isothermal heat flow on the wall, the
Angelberger model (Angelberger and Delhay, 1997) was employed to
calculate the heat transfer on the wall. Adaptive mesh refinement (AMR)
technique was used to reduce the meshing quantity based on the tem­
perature gradient of 1 K and velocity gradient of 1 cm/s. The compu­
tational mesh for a moment in the combustion process is shown in Fig. 6.

5. Numerical simulation conditions

Fig. 6. Grid structure at 45 ms during the combustion (N60R100, Φ = 0.4, T0

Hydrogen production of ammonia cracking is of great importance for
= 500 K, P0 = 2.0 MPa).
ammonia combustion, and in this study, it is considered that ammonia
cracking produces a 3:1 ratio of hydrogen to nitrogen. The heat of
combustion after complete cracking of ammonia for on-line hydrogen Table 2
production is 14.3% higher than that of pure ammonia. The combustion Initial conditions in 1D simulations.
characteristics for ammonia/methanol with ammonia cracking are
Variables Values
firstly studied under laminar burning condition at the initial tempera­
Initial temperature 298 and 500 K
tures of 298 and 500 K. The effects of methanol blends and ammonia
Initial pressure 0.1 and 0.5 MPa
cracking on LBV and NO emission under lean burn condition were Equivalence ratio 0.4–1.0
analyzed, and the detailed simulation conditions are listed in Table 2. Ammonia blending ratio 40% and 60%
The impact of ammonia cracking for lean burn extension was then Cracking ratio of ammonia 0%, 50%, 90%, and 100%
studied in 3D CFD simulation, and the simulation conditions are listed in
Table 3. The fraction of energy derived from ammonia was defined as

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X. Meng et al. Journal of Cleaner Production 450 (2024) 141959

Table 3 6. Results and discussion

Initial conditions in 3D numerical simulations.
Variables Values 6.1. Effect of methanol blends and ammonia cracking under laminar
burning condition
Initial temperature 500 K
Initial pressure 2.0 MPa
Equivalence ratio 0.4, 0.7, 0.8 The effects of methanol blends and ammonia cracking on LBV vari­
Ammonia blending ratio 60% ation under laminar burning condition were studied at 298 and 500 K as
Cracking ratio of ammonia 0%, 50%, 90%, and 100% presented in Fig. 7. As expected, a higher methanol blending ratio,
ammonia cracking ratio and initial temperature are beneficial for LBV
the percentage of the heat of combustion attributed to ammonia in the enhancement. LBVs of pure ammonia at ER of 1.0 and pure methanol at
total heat of combustion of both ammonia and methanol. The total en­ 0.9 and 1.0 under the same initial temperature and pressure are also
ergy remained equivalent to that of pure ammonia before the addition of compared as benchmarks. At 298 K, it presents that N40R100 and
methanol. The cracking ratios from 50% to 100% and ERs from 0.8 to N60R90 at ER of 0.7 yield the similar level of LBV as pure methanol at
0.4 were analyzed. To simplify the description, antonomasia was used, ER of 1.0. For a higher initial temperature at 500 K, ERs can be extended
where N60R90 represents an ammonia energy ratio of 60% in total to ER of 0.55 in N60R100 and 0.65 in N40R100. In comparison with
energy for ammonia/methanol blends and ammonia cracking ratio of pure ammonia at ER of 1.0, N60R90 and N60R100 at ER of 0.4 yield the
90%. similar LBV values at 298 K and much higher values at 500 K.
The hydrogen and nitrogen produced by ammonia cracking have
facilitating and inhibiting effects on LBV, respectively. While Fig. 7 re­
veals that the overall effect on LBV is positive when the cracking ratio is
increased. It incorporates the thermal effect of cracked gas addition as

Fig. 7. LBV comparison for methanol blends and ammonia cracking under laminar burning condition.

Fig. 8. Decoupling of the effect on LBV for methanol blends and ammonia cracking (P0 = 0.1 MPa, Φ = 0.6).

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X. Meng et al.
Fig. 9. Comparison of NO emission for methanol blends and ammonia cracking at 0.1 MPa.
well as the chemical and transport effects resulted from the variation in
fuel composition. Fig. 8 shows the simulation results of key radicals and
flame temperatures for the blended fuels of methanol and ammonia
cracking as well as the decoupling of the thermal effect on LBV. As
shown in Fig. 8a, the combustion temperature and the maximum mole
fractions of OH/H/O are increased with a higher ammonia cracking
ratio, which indicates that thermal and chemical effects play important
roles. To decouple the thermal effects, a similar approach as in the lit­
eratures (Mei et al., 2021) was used. Thermodynamic data of FN2
(C24H12) was used to replace a small fraction of N2 and excluded from
any chemical reaction. Fig. 8b shows the decoupling results of thermal
effects for ammonia cracking at two initial temperatures, ER of 0.6 and
0.1 MPa. The combustion temperature deviation of the fuel mixture
from the original NH3/CH3OH blends was controlled within ±1 K using
the virtual dilution gas method, thus eliminating the influence of ther­
mal effect. The disparity between the two LBV results represents the
chemical and transport effects. Additionally, the distinction between the
LBV of the cracked fuel blended with methanol and the calculated result
after applying the virtual dilution gas method signifies the thermal ef­
fect. The chemical and transport effects contribute more to the increase
in LBV. All these types of effects are increased gradually with the
increasing methanol blending and ammonia cracking ratios. In addition,
increasing the initial temperature also enhances these effects, especially
Fig. 10. Fuel and thermal NO variations using isotope labelling method (T0 = 500 K, Φ = 0.9).
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Journal of Cleaner Production 450 (2024) 141959
for the chemical and transport effects.
Fig. 9 shows the comparison of NO mole fraction for the two initial
temperatures. It shows that R50 in both N40 and N60 yields the highest
NO mole fraction for the same ER when it is higher than 0.5. R90 reveals
relatively lower level of NO mole fraction due to less ammonia fuel in
the mixture. Because of no fuel-NO generation, there is little NO in R100.
The trend demonstrates that lean-burn operation can significantly
reduce the NO emission even though with ammonia fuel. In comparison
with pure ammonia at ERs of 0.9 and 1.0, ammonia cracking leads to a
favorable level of NO below ER of 0.5 at 298 K. At 500 K, R90 at ER of
0.5 also presents an acceptable level of NO compared to pure ammonia,
especially for N40R90, while it characterizes much higher LBV than pure
ammonia at ER of 1.0 as shown in Fig. 7. Besides, the complete cracking
or partial cracking with ammonia separation should be favorable for the
NO control.
In order to distinguish the thermal and fuel NO formation with
ammonia in this work, isotopic labeling method was used to analyze the
source of NO. The N atom derived from air was labelled by N15 for all
the species and reactions containing N. After labelling, a mechanism
with 78 species and 559 reactions was formed. Fig. 10 shows the isotopic
labeling results of thermal and fuel NO mole fractions. As thermal NO
formation requires high combustion temperature with rich oxygen
condition, the analysis was conducted under the initial conditions of
X. Meng et al.
Fig. 11. Comparison of in-chamber pressure profiles between simulations and
measurements.
500 K and ER of 0.9. The initial pressures of 0.1 and 0.5 MPa were also
compared. As compared with the results in Fig. 9, the total NO mole
fraction is unchanged, indicating the accuracy of the calculation.
Fig. 10a shows that the proportion of thermal NO is less than 2% in total
at 0.1 MPa. The proportion increases to about 10% for thermal NO when
the initial pressure becomes 0.5 MPa, demonstrating that the initial
pressure has a great impact on the source of NO formation. However, it
could be noted that the increase of a higher initial pressure is beneficial
for the overall NO reduction. R0 and R50 shows slightly higher thermal
NO mole fraction at 0.5 MPa. In addition, it can be noted that the
increased initial pressure enhances the combustion temperature, which
also induces more formation of thermal NO.
Fig. 12. Comparison of temperature distributions in simulations and schlieren photographs in measurements.
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Journal of Cleaner Production 450 (2024) 141959
6.2. Visualization study and validation of 3D modelling
The combustion process for the ammonia/methanol and methanol/
hydrogen blends was experimentally studied in CVCC, and 3D CFD
modelling with the simplified mechanism was also validated as shown in
Fig. 11. A spark plug is installed on top of the chamber, and the flame
propagates downward. 80%ammonia/20%methanol, 60%ammonia/
40%methanol and 80%methanol/20%hydrogen were conducted and
compared, and it presents that both adding methanol and hydrogen can
significantly advance the peak pressure timing. 80%methanol/20%
hydrogen with a lower initial temperature and ER also reveals a much
more advanced peak timing. Overall, the pressure traces in numerical
simulations match the experimental data very well.
Fig. 12 shows the results of the schlieren images in the experiments
and cut-planes of temperature distributions in the simulations. Schlieren
image represents the gas density change caused by combustion. The
comparisons show that the flame propagation processes for experiments
and simulations are approximately identical. It can be found from the
schlieren structures that adding hydrogen induces a more intensive
wrinkle. The simulations reveal that a low ER generally leads to a lower
combustion temperature. Fig. 13 shows the results of measured and
simulated NO for ammonia/methanol blends at 140 ms. NO chem­
iluminescence measurements were conducted with constant trans­
mission gain, and the original image and pseudo-color image processed
via MATLAB code are presented. The cut-planes of NO distribution at the
center along the spark plug in simulations are also shown for compari­
son. 60%ammonia/40%methanol presents a smaller region with high
NO concentration, resulted from its earlier reduction process. However,
this does not represent the final NO results, as the NO reduction process
is still proceeded. It also shows that the simulations exhibit the accept­
able prediction for NO production. On the whole, the combination re­
sults in Figss. 11–13 reveal that the accuracy of the simulations with the
simplified mechanism is acceptable.
6.3. 3D simulation study of ammonia cracking in lean burn condition
Based on the 3D CFD modeling validations, this section discusses the
X. Meng et al. Journal of Cleaner Production 450 (2024) 141959

Fig. 13. Comparison of measured and simulated NO distributions at 140 ms.

impact of ammonia cracking on combustion and NO with ammonia/

methanol blends for lean-burn expansion. The initial conditions are
shown in Table 2, R50, R90 and R100 at ER of 0.4 are compared with R0
at ERs of 0.7 and 0.8 for 60%ammonia/40%methanol (N60). Fig. 14
presents the in-chamber pressure and heat-release rate (HRR)

Fig. 14. Variations of in-chamber pressure and HRR for various cracking ratios
and ERs.
Fig. 16. Comparisons of combustion phasing and duration for various cracking
ratios and ERs.

Fig. 15. Temperature distribution for various cracking ratios and ERs.

9
X. Meng et al.
Fig. 17. Mass fraction distribution of NH and HNO for various cracking ratios and ERs.
comparisons, and it reveals that the times of peak pressure in N60R90
and N60R100 at ER of 0.4 are closed to that in N60R0 at 0.8 and much
more advanced than that at 0.7. The HRR trend reveals that the peaks in
N60R90 and N60R100 appear slightly earlier than that in N60R0 at 0.8,
while they reveal slightly longer tails of HRR. N60R50 at 0.4 reveals a
similar peak time of HRR as N60R0 at 0.7, but also yielding a longer tail.
Fig. 15 shows the cut-planes of in-chamber temperature distribution
along the center of spark plug. As expected, a lower ER of 0.4 yields a
much lower combustion temperature, especially for N60R50. A lower
combustion temperature can inhibit the thermal NO formation, and
adding hydrogen by ammonia cracking with a lower ER can maintain
the combustion rate and lower the combustion temperature
simultaneously.
Fig. 16 shows the combustion phasing and duration variations with
different cracking ratios and ERs. The percentage of mass fraction
burned (MFB) is compared as combustion phasing. MFB10 and MFB50
are similar for N60R90 and N60R100 at 0.4, N60R0 at 0.8. However,
MFB90 is delayed in both N60R90 and N60R100, resulting in longer
combustion durations compared to N60R0 at 0.8. Despite this, their
combustion durations are still much shorter than N60R0 at 0.7. Addi­
tionally, all the MFBs are retarded in N60R50 compared to N60R0 at 0.7,
while its combustion duration is slightly longer than N60R0 at 0.7.
Fig. 17 shows a comparison of the distributions of NH and HNO.
HNO directly contributes to NO formation during combustion, and NH
has a significant effect on NO reduction reaction. For NH, it firstly ap­
pears in the flame front area as shown at 45ms. At 90 ms, N60R0 at 0.8
presents much higher NH concentration in the early burned zone. At this
time, NH in N60R0 at an ER of 0.7 and N60R50 at 0.4 is still mainly
distributed in the flame front, and N60R90 at 0.4 reveals much less NH
formation in the flame front due to less ammonia fuel. At 120 ms, N60R0
at 0.7 also leads to a certain amount of NH in the early burned zone,
which reflects that equivalence ratio has a great impact on NH forma­
tion. At 200 ms, almost no NH can be found in N60R50 and N60R90, and
a small amount of NH can still be found in the non-cracked fuel blends.
As both of them are mainly converted from NH2 simultaneously, the
region for the HNO formation is similar as that of NH, and it also initially
apprears in the flame front area at 45 ms. Subsequently, in N60R0 at 0.7
10
Journal of Cleaner Production 450 (2024) 141959
and 0.8, there is a greater increase in HNO formation in the burned
region. However, N60R50 and N60R90 consistently show minimal HNO
formation in the burned region.
Fig. 18 presents the variations of NH2, NH and HNO mass fractions
with time for different cracking ratios and ERs. The total quantities of
these three species are primarily affected by ER and cracking ratio,
which also reflects the magnitude of their peak values. As no ammonia
fuel in N60R100, there is no NH2, NH or HNO generation. NH2 is a
product of ammonia pyrolysis, and its trend is generally consistent with
the variation in HRR. A higher ER and lower cracking ratio lead a higher
peak of NH2. Consequently, a higher NH2 peak also results in higher NH
and HNO peaks. The overall amount of NH and HNO formation is
relatively lower in N60R50 and N60R90.
Fig. 19 presents the cut-planes of NO distributions for different
cracking ratios and ERs. At 45 ms, N60R0 at 0.7 and 0.8 reveal higher
NO concentrations in the burned region. By 90 ms, a large amount of NO
is generated in N60R0 at 0.8, and it continues to have more NO than that
at 0.7 at 120 ms. However, at 200 ms, N60R0 at 0.8 presents much less
NO distribution than N60R0 at 0.7, which is primarily due to its more
efficient NO reduction process. for an ER of 0.4, N60R90 presents the
highest NO concentration within 200 ms, and N60R100 yields much
lower NO mass fraction comparatively due to the absence of fuel-NO
formation.
Fig. 20 shows the NO mass fraction comparisons with time, and the
results for pure ammonia combustion at 300 ms with ERs of 0.8–1.0 is
also presented as the baseline. It can be found that N60R0 at 0.7 and 0.8
reveal much higher levels of NO, whereas an ER of 0.4 with the ammonia
cracking leads to lower NO formation. N60R0 at 0.8, which yields more
NH and NH2 formation, exhibits a higher reduction ability compared to
N60R0 at 0.7, leading to a lower NO generation at 300 ms. On the other
hand, N60R50 and N60R90, having less NH and NH2 generation, reveal
a weakened NO reduction process in the later stages. N60R50 leads to
slightly lower NO than N60R90 due to its lower combustion tempera­
ture, while its combustion duration is too long. Moreover, N60R100
without fuel-NO formation reveals a much lower level of NO generation
throughout the process. Overall, NO emission in N60R90 at an ER of 0.4
is 59.8% lower than that in N60R0 at an ER of 0.8 and 64.5% lower than
X. Meng et al.
Fig. 18. The variation characteristics of NH2, NH and HNO species with time.
that in N60R0 at an ER of 0.7.
7. Conclusions
Ammonia/methanol blended fuel combined with ammonia cracking
under lean-burn condition was numerically and experimentally studied
in this work. Firstly, the previous mechanism with 59 species and 344
reactions was simplified to a new one with 42 species and 200 reactions.
Visualization measurements for schlieren and NO chemiluminescence in
CVCC were carried out, and the combustion pressure evolution was also
tested. The 3D modeling with the simplified mechanism was performed
based on the experimental data. The impacts of methanol addition and
ammonia cracking on combustion process and NO generation under
lean-burn operation were analyzed further, and the main findings can be
summarized as follows.
The analyses in laminar burning condition at 298 and 500 K showed
that ammonia cracking has a substantial impact on extending the lean-
burn limit. At 298 K, N60R90 at ERs of 0.7 and 0.4 can obtain the similar
LBVs as pure methanol and ammonia at 1.0, respectively. Furthermore,
the lean-burn operation with ammonia cracking can be further extended
at 500 K. Notably, the combustion with ammonia cracking at lower ERs
can also obtain the favorable level of NO emission.
The visualization measurements in CVCC revealed that adding
methanol or hydrogen enhances the combustion intensity, especially for
11
Journal of Cleaner Production 450 (2024) 141959
hydrogen addition. The 3D simulation of ammonia cracking at different
ERs showed that N60R90 and N60R100 at 0.4 lead to an equivalent level
of combustion rate as N60R0 at 0.8 and are much higher than that at 0.7.
Additionally, ammonia cracking at 0.4 reveals much lower NO
compared to non-cracking condition at 0.7 and 0.8. N60R90 at 0.4 yields
a similar level of NO to pure ammonia at 1.0. N60R100 can further
reduce the NO emission due to the absence of fuel-NO formation in lean-
burn operation.
In summary, ammonia/methanol combustion with a relatively high
ammonia cracking ratio at lower ERs is advantageous for the improve­
ments of both the combustion rate and NO reduction.
CRediT authorship contribution statement
Xiangyu Meng: Conceptualization, Supervision, Writing – review &
editing, Funding acquisition. Lizi Liu: Data curation, Writing – original
draft. Meichao Qin: Software, Validation. Menglan Miao: Investiga­
tion. Hang Zhao: Visualization. Wuqiang Long: Writing – review &
editing. Mingshu Bi: Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
X. Meng et al. Journal of Cleaner Production 450 (2024) 141959

Fig. 19. NO mass fraction distribution for various cracking ratios and ERs.

the work reported in this paper.

Data availability

Data will be made available on request.

Acknowledgments

This work is supported by the National Key R&D Program of China

(No.2021YFB4000904), the National Natural Science Foundation of
China (Grant No.52171296), and the Fundamental Research Funds for
the Central Universities (Grant Nos.DUT22GF302 and DUT22QN248).

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.

org/10.1016/j.jclepro.2024.141959.

Fig. 20. Evolution process of NO mass fraction with time for various cracking
ratios and ERs.
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