fmech-08-944201

REVIEW
published: 22 July 2022

doi: 10.3389/fmech.2022.944201
Ammonia as Green Fuel in Internal

Combustion Engines: State-of-the-Art
and Future Perspectives
Cinzia Tornatore, Luca Marchitto *, Pino Sabia and Mara De Joannon
STEMS-CNR, Institute of Science and Technology for Sustainable Energy and Mobility, Italian National Research Council, Napoli,
Italy
Ammonia (NH3) is among the largest-volume chemicals produced and distributed in the
world and is mainly known for its use as a fertilizer in the agricultural sector. In recent years,
it has sparked interest in the possibility of working as a high-quality energy carrier and as a
Edited by: carbon-free fuel in internal combustion engines (ICEs). This review aimed to provide an
Evangelos G. Giakoumis, overview of the research on the use of green ammonia as an alternative fuel for ICEs with a
National Technical University of
Athens, Greece
look to the future on possible applications and practical solutions to related problems. First
Reviewed by:
of all, the ammonia production process is discussed. Present ammonia production is not a
José V. Pastor, “green” process; the synthesis occurs starting from gaseous hydrogen currently produced
Universitat Politècnica de València,
from hydrocarbons. Some ways to produce green ammonia are reviewed and discussed.
Spain
Jinlong Liu, Then, the chemical and physical properties of ammonia as a fuel are described and
Zhejiang University, China explained in order to identify the main pros and cons of its use in combustion systems.
Qinglong Tang,
King Abdullah University of Science
Then, the most viable solutions for fueling internal combustion engines with ammonia are
and Technology, Saudi Arabia discussed. When using pure ammonia, high boost pressure and compression ratio are
*Correspondence: required to compensate for the low ammonia flame speed. In spark-ignition engines,
Luca Marchitto
adding hydrogen to ammonia helps in speeding up the flame front propagation and
luca.marchitto@stems.cnr.it
stabilizing the combustion. In compression-ignition engines, ammonia can be successfully
Specialty section: used in dual-fuel mode with diesel. On the contrary, an increase in NOx and the unburned
This article was submitted to NH3 at the exhaust require the installation of apposite aftertreatment systems. Therefore,
Engine and Automotive Engineering,
a section of the journal the use of ammonia seems to be more practicable for marine or stationary engine
Frontiers in Mechanical Engineering. application where space constraints are not a problem. In conclusion, this review
Received: 14 May 2022 points out that ammonia has excellent potential to play a significant role as a
Accepted: 17 June 2022
sustainable fuel for the future in both retrofitted and new engines. However, significant
Published: 22 July 2022
further research and development activities are required before being able to consider
Citation:
Tornatore C, Marchitto L, Sabia P and large-scale industrial production of green ammonia. Moreover, uncertainties remain about
De Joannon M (2022) Ammonia as ammonia safe and effective use and some technical issues need to be addressed to
Green Fuel in Internal Combustion
Engines: State-of-the-Art and overcome poor combustion properties for utilization as a direct substitute for standard
Future Perspectives. fuels.
Front. Mech. Eng 8:944201.
doi: 10.3389/fmech.2022.944201 Keywords: ammonia, green fuel, internal combustion engine, decarbonization, combustion
Frontiers in Mechanical Engineering | www.frontiersin.org 1 July 2022 | Volume 8 | Article 944201

Tornatore et al. Ammonia Green Fuel
1 INTRODUCTION
The increase in the overall temperature on and above Earth’s
surface represents one of the key issues we need to face in the next
future. Our planet’s climate is significantly changing mainly due
to human activities, and the transportation sector plays a
significant role in this global warming. Therefore, at the
moment, actions to mitigate the effects of transport on the
Earth’s atmosphere are extensively studied and analyzed.
Along with the electrification of the sector, manufacturers and
researchers are exploring alternative and advanced fuels that may
represent an efficient way to reduce global CO2 emissions when
assessed on a well-to-wheels basis. FIGURE 1 | Scheme of a typical Haber–Bosch process.
Moreover, the very unstable equilibrium of the world political
situation makes it increasingly necessary to untie the transport
sector from fossil fuels. optimization of the catalyst and reaction processes will be
In this scenario, new carbon-free fuels attainable from required to ensure that the energy losses from the ammonia
renewable sources are of increasing strategic relevance. decomposition reaction are close to the theoretical minimum
Ammonia is a versatile chemical, composed of nitrogen and value of approximately 7% of the energy stored in the ammonia
hydrogen (NH3). It is mainly known for its use as a fertilizer in the molecule (Lamb et al., 2018).
agricultural sector, but it is also widely adopted as a base for In addition, ammonia can be directly used as a fuel in
chemical synthesis or involved as a molecule in many processes in combustion systems and, in particular, in internal combustion
different fields. For example, it is an intermediate in the synthesis engines. This study examines precisely the potential of ammonia
of sodium bicarbonate, explosives, nylon and synthetic fibers, as an engine fuel. First of all, the ammonia production process is
plastics, and polymers; a component for paints, hair dyes, and briefly discussed with more emphasis on new ways to produce
household cleaner; a refrigerant; a solvent; a whitener in the paper green ammonia. The chemical and physical properties of
industry; a stabilizer in the rubber industry; a reducing agent in ammonia as a fuel are described and explained in order to
metallurgy; and a reagent for the control of nitrogen oxides identify the main pros and cons of its use in internal
(NOx) in the exhaust of diesel engines in aqueous solutions. combustion engines. Then, the most viable solutions for
For this reason, ammonia is among the largest-volume chemicals powering internal combustion engines with ammonia are
produced in the world (USGS (2021) Nitrogen Statistics and discussed.
Information).
In recent years, ammonia has attracted interest because of the
possibility of working as a hydrogen carrier and a carbon-free 2 AMMONIA PRODUCTION PROCESS
fuel. It can be defined as a hydrogen carrier due to its remarkably
high hydrogen density. Indeed, it contains 1.5 mol of molecular The synthesis of ammonia occurs starting from gaseous hydrogen
hydrogen for each mole. It is well known about the importance and nitrogen according to the direct reaction in the gaseous
of hydrogen in the transition toward the decarbonization of the phase:
transport sector (Capurso et al., 2022; Zhang et al., 2022). 3H2 + N2 → 2 NH3.
However, hydrogen storage remains a major challenge, The reaction is reversible and exothermic with
limiting its direct application to vehicles: It must be stored ΔH = −92.4 kJ/mol.
at −253°C as a liquid or at pressures of about 700 bar as a gas. The main process for ammonia production is the
Liquid ammonia, on the other side, can be stored at a reasonable Haber–Bosch (H-B) one in which the reaction takes place in
temperature of -33°C at standard pressure and +20°C at 9 bar. the presence of catalysts, at a pressure of 200 atm and a
This makes the storage and transport of this energy carrier temperature of 400–450°C. Figure 1 shows a simplified
much easier. Hydrogen production from ammonia has been scheme of a typical Haber–Bosch process. Suitable catalysts are
widely studied. It can be obtained through thermal based on osmium, ruthenium, uranium, or iron, even though the
decomposition or catalytic cracking of ammonia into latter is generally used, preparing the catalyst starting from
nitrogen and hydrogen and electrolysis or electro-oxidation. magnetite. The H-B process is a closed-loop process, where
Ammonia decomposition is a slow reaction with a very high the ammonia is separated from the product stream by cooling
energy requirement, and metal catalysts are often used to speed and further condensation. Next, the unreacted synthesis gas is
up hydrogen production. Much research has been devoted to mixed with the fresh feed and sent back to the ammonia synthesis
developing suitable catalysts for this purpose. It is widely agreed reactor (Rossetti, 2020).
that low-available ruthenium is the best catalyst for The Haber–Bosch process has been optimized over the past
decomposition at 400°C, since it is highly active (Ashik et al., century, starting with an energy consumption of about 100 GJ/
2018). The widely available less expensive Ni-based catalysts tNH₃ in the 1930s down to about 26 GJ/tNH₃ today
perform comparably at 600°C. Further cost reductions and (Rouwenhorst et al., 2021).

There are also alternative processes (Fauser, Casale, Claude, 2.1.1 First Route: Renewable Sourced Hydrogen +
NEC, Mont-Cenis, etc.), which differ in the pressure at which the Haber–Bosch Process
reaction takes place and therefore in the synthesis apparatus. One way to synthetize green ammonia is to use hydrogen
For all these processes, nitrogen (large-scale production) is produced by renewable sources and nitrogen produced in the
obtained by rectification of liquid air produced with “Linde” or air separation unit (ASU). These are then fed into the
with “Claude” processes (Agrawal and Woodward, 1991). Haber–Bosch process, all powered by sustainable electricity
Moreover, technologies such as pressure swing adsorption or (Valera-Medina et al., 2018).
membranes can be used for smaller production capacities The most established technology to produce hydrogen from
(Sánchez and Martín, 2018). renewable sources is water electrolysis even if, at present, only 4%
Hydrogen used as a reagent is currently mainly produced from of hydrogen can be obtained in this way mainly due to economic
natural gas, which can be subjected to steam reforming or issues (Shiva Kumar and Himabindu, 2019). Figure 2 shows a
alternatively to an autothermal process; the latter is a cheaper scheme of green ammonia production through electrolysis and
method from a plant engineering point of view and involves partial H-B process. Electrolysis consists of splitting water molecules to
oxidation of the hydrocarbon into carbon monoxide and hydrogen produce hydrogen and oxygen as a by-product using an electric
using an appropriate amount of air, in a muffled oven above current. A water electrolysis cell consists of two electrodes
1,000°C in the presence of an oxide-supported nickel catalyst of separated by an electrolyte that is the medium responsible for
magnesium. A lower percentage of hydrogen is produced through transporting the generated chemical charges [anions (-) or
coal gasification, which is significantly more emission-intensive cations (+)] from one electrode to the other. Water electrolysis
than natural gas-based production. Most of the ammonia can be classified into four types based on the type of electrolyte:
production from coal takes place in China. About 85% of the
country’s ammonia production occurs through coal gasification. • Alkaline water electrolysis (AWE),
Much smaller amounts of ammonia are produced through coal • Proton exchange membrane (PEM) water electrolysis,
gasification in the United States, South Africa, and Indonesia. In • Solid oxide electrolysis (SOE), and
2020, of the 185 Mt of ammonia produced, 72% relied on natural • Microbial electrolysis cells (MEC).
gas–based steam reforming, 26% on coal gasification, and about 1%
on oil products. These numbers indicate that currently, ammonia is The electrolyzer is composed of the stack (where the actual
primarily produced from fossil fuels (called “gray ammonia”): This splitting of water into hydrogen and oxygen takes place) and the
kind of production requires high energy (~28–33 GJ/tNH3) and rest of the plant, which comprises power supply, water supply and
produces high CO2 emissions [~1.6 tCO2/tNH3, about 1.8% of purification, compression, possibly electricity and hydrogen
global carbon dioxide emissions (The Royal Society, 2020)] mainly buffers, and hydrogen processing (Yue et al., 2021).
due to the energy- and carbon-intensive reforming process to The most common and commercially viable electrolyzers are
produce hydrogen (Tock et al., 2015). based on PEM and AWE, classified as low-temperature
Ammonia is defined as “blue” when carbon capture and electrolyzers since they operate between 30°C and 80°C. SOE
storage (CCS) systems are included in its production. CCS cells perform a high-temperature electrolysis ranging between
technologies are expected to increasingly contribute to cleaner 800 and 1,000°C. They are also under development but have yet to
energy transitions by significantly reducing CO2 emissions from be deployed at scale.
point sources on a large scale, including power generation plants Microbial electrolysis cells (MEC) are an emerging
and industrial plants using fossil fuels or biomass. Globally, this bioelectrochemical technology to produce H2 from organic
can mitigate the increase in CO2 emissions, but these technologies matter. MEC technology is very suitable and has the potential
are at an early stage of research and development, so they are not for effective energy production in waste biorefineries (Mallick
ready for commercialization and are not cost-effective et al., 2022).
(Mallouppas et al., 2022). To take electrolysis from niche to mainstream, from potential
When ammonia is synthesized only from renewable energy sources, to reality, research is focusing on overcoming current challenges.
it is named “green” ammonia. It is predicted that the global green The first goal is to reduce the cost of green hydrogen produced in
ammonia market will rapidly grow, at a compound annual growth rate this way: The European Commission (European Commission,
of 7.8%, from 2021 to 2027 (Han et al., 2022), which could reduce the 2021) recently indicated that our target should be €1.8/kg by
dependence of ammonia production on fossil fuels. 2030, while currently (in 2020), the cost of hydrogen produced
through water electrolysis powered by renewable electricity is
2.1 Production of Green Ammonia estimated to be €6/kg. This drastic reduction can be achieved
There are two different routes to produce green ammonia: The through a better understanding of the trade-offs in performance,
first one, of considerable long-term scope, is based on the cost, and durability of electrolyzer systems in predicted future
Haber–Bosch process fed with hydrogen from renewable dynamic modes of operation using CO2-free electricity such as
sources (green hydrogen), and the entire process is powered the one generated by solar, wind, and hydropower resources. At
by fully renewable electricity. The second path is based on the the same time, the capital cost of the electrolyzers unit (stack) and
electrochemical ammonia synthesis; in this case, the H-B process of the rest of the plant should be reduced. The greatest potential
is no longer required. for short-term cost reduction is in the rest of the plant, while in a

FIGURE 2 | Green ammonia production through electrolysis of water + Haber–Bosch process.
long-term perspective, it is mandatory to reduce the capital cost 2.1.2 Second Route: Electrochemical Ammonia
of the stack. Furthermore, RD&D is called to show the way to Synthesis
improve energy efficiency for the conversion of electricity to The electrochemical ammonia synthesis (EAS) has attracted a lot
hydrogen in a wide range of operating conditions, to deepen the of attention in the present century as it does not involve carbon
understanding of the degradation processes of electrolytic cells emissions and the optimal operating conditions require
and the stacks, and to develop mitigation strategies to increase atmospheric temperature and pressure (Shen et al., 2021). The
stack operational life (IRENA—International Renewable Energy very unsustainable H-B process is not required, and the EAS can
Agency, 2020). be driven by renewable electrical energy generated by solar, wind,
An alternative way to produce green hydrogen that can be or hydropower. EAS mainly consists of electrochemical N2
coupled to the H-B process for ammonia production is biomass reduction reaction (NRR) to produce NH3; H-source is
gasification, a thermochemical process that converts biomass into ultimately water.
hydrogen and other products (CO, CO2, CH4, and N2) without There are different modes of this process being actively
combustion. This process is carried out under substoichiometric researched:
conditions, by causing a gasification agent to flow into the reactor,
which reacts with the biomass. The most commonly used (1) the electrochemical nitrogen reduction reaction (eNRR) in
gasification agent is air; however, to increase the H2 content which an electrocatalyst enables direct electron and proton
and avoid dilution of N2, other gases can be used, namely O2, addition to the N2 molecule,
steam, or a combination thereof (Piazzi et al., 2022). Today, no (2) indirect or mediated NRR mechanisms in which a redox
plant is operated using this technology due to its high expected mediator is first reduced and then, via a series of reactions,
costs and low technological maturity. Framework conditions are ammonia is produced and the mediator is regenerated.
yet missing for biomass gasification-based hydrogen production Recently, lithium-mediated electrochemical NRR has
to be economically competitive with fossil-based hydrogen received renewed attention due to its reproducibility.
production (IEA Bioenergy et al., 2018). Lithium-mediated NRR begins with electrochemical
In the first route of green ammonia production, it is necessary deposition of lithium, followed by two chemical processes
to consider that the Haber–Bosch process integrated with water of dinitrogen splitting and protonation to ammonia (Cai
electrolysis and powered by renewable electricity will need a new et al., 2021).
optimization. To enable electrically operated H-B systems to cope
with the geographically isolated and intermittent nature of Significant and encouraging progress has been made in the
renewable energy, small-scale processes with low capital costs electrochemical nitrogen reduction reaction (NRR) under
and simple operation and control, capable of agile and adjustable ambient conditions over the past 5 years. This process would
operation, could be designed. Developing more active H-B be ideal for distributed generation and more amenable to
catalysts would facilitate operation under milder conditions intermittent power supplies. However, to date, only low rates
and reduce energy demand, making the process more of ammonia production have been demonstrated in laboratory
amenable to variable and smaller-scale operations (Smith and studies. This process is currently at TRLs 1–2; key challenges
Torrente-Murciano, 2021). Moreover, ideally the H-B process remain that need to be addressed. Although thermodynamically
runs continuously, a feature that contrasts with the intermittent feasible, high overpotentials are generally required to overcome
supply of solar or wind electricity: This could be addressed the kinetic barrier of the strong N–N triple bond. Both the yield
through the creation of an intermediate energy storage rate and the Faradaic efficiency (FE) toward NH3 formation are
solution (MacFarlane et al., 2020). low. The large overpotential and low NH3 selectivity intensify the

TABLE 1 | Combustion properties of NH3 and other hydrocarbon fuels.
Fuels Heating value Energy density Density Octane Flame velocity Flammability limits Minimum
[MJ/Kg] [MJ/L] [kg/m3] [RON] [m/s] [vol/%] ignition
energy [mJ]
NH3 cooled and 18.6 12.69 1 atm -33°C 682 >130 0.067 15–28 680
liquefied
NH3 compressed and 11.65 300 atm 25°C 626
liquefied
H2 cooled and liquefied 120 8.5 1 atm -253°C 70.85 >130 3.25 4.7–75 ~0.016
H2 compressed and 2.46 300 atm 25°C 20.54
Gasified
Diesel n-dodecane 44.11 32.89 1 atm 25°C 745.7 <20 ~0.80 0.43–0.6 ~0.23
Gasoline iso-octane 44.34 n-octane 30.93 n-octane 100 0.41 0.6–8 ~0.14
1 atm 25°C 697.6
Methanol 19.90 15.65 1 atm 25°C 786.3 108.7 0.56 6.7–36 0.14
Ethanol 26.84 21.07 1 atm 25°C 785.1 108.6 0.58 3.3–19 0.6
problem of energy efficiency. Another fundamental issue is the Ammonia oxidation properties, along with the comparison of
durability of the NRR process: Stability tests reported in the common fuels for ICEs, congruently reported to highlight its
scientific literature are commonly below 20 h, too short a problematic issues, are reported in Table 1 (readapted from
duration for the industrial implementation where thousands of https://www.iea-amf.org/content/fuel_information/ammonia).
hours of stable operation at high current density are expected. Table 1 reports parameters relevant to ICEs, in terms of fuel
Therefore, future protocols for catalyst durability need to aim for energy content as lower heating value (LHV), in both the
much longer test durations. It is also necessary to work toward gravimetric and the volumetric form (MJ/Kg and MJ/L,
understanding catalyst degradation mechanisms. To promote respectively), fuel density (Kg/m3), octane number (RON),
electrochemical synthesis, catalyst and electrolyte should flame velocity (m/s), flammability limits (vol%), and minimum
always be considered and optimized together (Shen et al., 2021). ignition energy (MIE, mJ). NH3 is considered in the liquified
There are several other ongoing studies on the scientific form, cooled at atmospheric pressure and T = −33°C, or
community for green ammonia synthesis such as pressurized at typical vessel conditions (300 bar) and at 25°C,
electrochemical synthesis from nitric oxide (Long et al., 2020), to easily compare with liquefied or compressed hydrogen, at the
electrochemical production through photoelectrochemically same reference pressure. For comparison, diesel, such as
produced hydrogen under concentrated sunlight (Yusuf and n-dodecane, and gasoline, such as iso- or n-octane, are
Ibrahim, 2017), photo-electrochemical synthesis (Boucher considered as conventional fuels in ICEs. The analysis is then
et al., 1995; Martín et al., 2019), ammonia synthesis using extended to alcohols, such as methanol and ethanol, as relevant
nitrogenase organisms and biomimetic catalysts to create a low-carbon fuels in ICEs, producible from renewable resources.
biotechnological route (Chen et al., 2020), and Among the considered fuels, NH3 has the lowest LHV in terms
electromagnetic-induced (Ghassan and Ibrahim, 2020) of MJ/Kg, comparable only with alcohols, as partially oxidized
ammonia synthesis (Chehade and Dincer, 2021). All these species, while H2, on a weight basis, has an energy content of
processes are currently at TRL 1; further research and 120 KJ/Kg, almost three times greater than gasoline and diesel
development would be required before large-scale industrial (~44 MJ/Kg). If the energy content is then expressed in terms of
production could be considered. volume (MJ/L), H2 has the lowest energy density, both in
pressurized (2.46 MJ/L) or in liquefied (8.5 MJ/L) forms,
highlighting main concerns related to H2 storage and
3 CHEMICAL AND PHYSICAL PROPERTIES transportation. Apart from safety reasons, the compression
OF AMMONIA AS A FUEL work of H2 is extremely high, about 1.05 kWh/kg H2 from
20 to 300 atm, while H2 cryogenic liquefaction at −253°C
3.1 NH3 Chemical and Physical Properties requires 2.88 kWh/Kg (Gardiner and Satyapal, 2009). In turn,
Ammonia has been identified as a high-density and safely NH3 has an energy content equal to 12.69 MJ/L in the cooled
transportable hydrogen carrier to use in energy production liquified form, and 11.65 MJ/L if liquefied by compression. The
and transportation systems, which may promptly respond to conversion from gravimetric to volumetric energy contents
environmental policies conceived to decarbonize energy passes through the fuel density, thus highlighting the very low
production chains. In contrast to hydrogen, the main hydrogen density, while conferring to NH3 the property of a high
advantage consists of available storage/transportation H2-density vector.
infrastructures, developed over the time to deliver ammonia as The main practical issues related to NH3 as a fuel in
a chemical. Albeit with these advantages, some crucial drawbacks combustion systems are related to its poor ignition quality
exist, for the combustion-based system, due to NH3 chemical/ (RON>130), with a high autoignition temperature (924 K), low
physical properties. flame speed (~7 cm/s for a stoichiometric NH3/air mixture, P =

1 atm, T = 298 K), about one order of magnitude lower with utilization can be drawn up. As a relevant parameter to
respect to conventional fuels and alcohols, and 3 with respect to combustion application, ICE and gas turbines, the laminar
H2. Then, its narrow flammability limits (15%–28% by volume in flame speed (SL) of NH3 has been experimentally characterized
air) and a very exceptional high minimum ignition energy (MIE = over the years with respect to mixture equivalence ratio (φ)
680 mJ), with respect to the other considered fuels (see Table.1), (Figure 3) (Zakaznov et al., 1978; Ronney and Wachman,
complete the picture of NH3 combustion properties. 1985; Pfahl et al., 2000; Jabbour and Clodic, 2004; Takizawa
In addition, it is worth mentioning NH3 has a high latent heat et al., 2008; Li et al., 2014; Hayakawa et al., 2015; Han et al., 2019;
of vaporization (1370 KJ/Kg). For instance, ethanol, liquid H2, Mei et al., 2019; Lhuillier et al., 2020a; Lubrano Lavadera et al.,
and gasoline have a latent heat of vaporization equal to 840, 445.6, 2020).
and 305 KJ/Kg, respectively. This implies that if NH3 is injected The NH3/air laminar flame speed versus φ at 298 K and
into engines, combustion temperature may drastically decrease, 1 atm are in-between 1.4 and 8.23 cm/s for φ in the range
causing incomplete combustion and loss of engine efficiency 0.7–1.3. SL increases with φ from fuel-lean to fuel-rich
(Okafor et al., 2021). conditions and peaks at around φ = 1.1, where the
The high NH3 RON value may be conceived as an advantage maximum values vary from 6.3 to 8.2 cm/s. As expected, it
for SI engines, as its high anti-knocking tendency can result in decreases with a further increase in φ. Small differences are
higher compression ratios (CR) and thus in an engine efficiency identifiable for fuel-lean mixtures, while the discrepancy
increase (Cornelius et al., 1966). among experimental data increases for fuel-rich conditions,
Regarding NOx emissions, the high tendency to fuel NOx with a maximum difference of about 2 cm/s.
formation from NH3 oxidation has to be properly chamfered, Hayakawa et al. (2015) demonstrated that for NH3/air
through the implementation of primary (air-fuel staging, flue gas mixture, an increase in the pressure from 1 to 5 atm decreases
recirculation, and humidification) or post-combustion the laminar flame speed, almost linearly with P. For instance, for
techniques [selective non-catalytic reduction (SNCR) and φ = 1, it decreases from 7 cm/s down to about 5 cm/s.
selective catalytic reduction (SCR)] (Skalska et al., 2010). Such a low laminar flame speed may hinder the direct use of
From a chemical point of view, many of these characteristics NH3 in ICEs; thus, several strategies have been proposed to
derive from its molecular structure. NH3 has a trigonal pyramidal increase this crucial parameter. First, the SL has been
shape, similar to methane, with a central nitrogen covalently experimentally characterized for preheated NH3/air mixture.
bonded with three hydrogen atoms and an unshared pair of Han et al. (2019) and Lhuillier et al. (2020b) reported data
electrons. The covalent N-H bond nature implies a high with preheating the mixture up to 448 and 473 K, respectively.
dissociation energy, which reflects in NH3 lower reactivity Restricting the analysis to the stoichiometric NH3/air mixture, SL
with respect to the standard fuels in combustion systems. increases almost linearly with T, up to 14 cm/s for T = 448 K.
The structure with the lone pair, which easily accepts a proton, Common strategies to improve NH3 oxidation properties rely
gives an alkaline characteristic to ammonia. On the contrary, the on the use of fuel “enhancers,” such as H2, CH4, syngas, and other
trigonal pyramidal asymmetrical shape, with nitrogen much conventional or e-fuels (Pfahl et al., 2000; Okafor et al., 2018; Han
more electronegative than the three H atoms, makes ammonia et al., 2019; Lubrano Lavadera et al., 2020; Wang et al., 2020;
a molecule with a strong polarity, even higher than water. This Wang et al., 2021; Ariemma et al., 2022), in compliance with
yields to a highly hygroscopic characteristic that causes the energy production decarbonization strategies, or modifying the
formation of moistures, possibly very corrosive on metals, environmental atmosphere toward O2-enriched conditions. H2
especially on copper and brass, commonly used in ICEs as can also be produced directly through NH3 partial catalysis (Li
gaskets. et al., 2014) techniques, prior to the injection in combustion
The strong polarity of ammonia also significantly affects its systems. Further options to improve NH3 oxidation features
oxidation kinetics, as it will be discussed in the following. In could come through the implementation of plasma-assisted
addition, NH3 under oxidative conditions may lead to systems (Choe et al., 2021).
conspicuous emissions of fuel NOx; thus, the comprehension Limiting the analysis to H2, CH4, and alcohols as fuel
of NH3 ammonia chemistry and NOx formation routes is of enhancers from recent studies, in Figure 4 the ammonia
paramount relevance to opportunely tune system operating laminar flame speed is reported as a function of the “fuel
conditions to ensure ammonia full conversion while reducing enhancer” concentration (reported as %) or for O2-enriched
the risk of NOx emissions. environments for a stoichiometric NH3/O2 flame. For the O2-
From an organoleptic point of view, ammonia is a colorless enriched environment, the O2 concentration has to be read as a
gas, with a sharp smell. This is an advantage with respect to its surplus with respect to the “air” condition.
toxicity. Indeed, a possible leakage is easily perceived (at about The case of H2 as a “fuel enhancer” is reported on both the
5 ppm), well before reaching the safety levels, fixed at 25 and primary axis, up to a H2 concentration of 45%, to highlight some
35 ppm, respectively, as short-term and time-weighted average peculiar features, and the secondary axis, as the pure H2 laminar
exposure limits (New Jersey Department of Health, 2016). flame speed is 1 order of magnitude greater than the other pure
Laminar burning speed (SL) and ignition delay times are target “fuel” enhancers.
parameters for ICEs. Restricting the analysis to SL, as a It is possible to note that the addition of H2 or CH4 (Han et al.,
comprehensive parameter representative of characteristic 2019), and CH3OH or C2H5OH (Wang et al., 2021) notably
chemical timescales, some consideration on the NH3 ammonia increases the NH3 laminar burning velocity. For instance, H2

FIGURE 3 | NH3/air laminar burning velocities vs. mixture equivalence ratio (φ) at 298 K and 1 atm.
FIGURE 4 | SL as a function of the fuel “enhancer” addition (reported as %) or of the O2 content.
(rhombus), CH4 (dot), and alcohols (squares) increase the concentration (Mei et al., 2019), starting from the “air” condition
ammonia SL almost equally up to a relative concentration of (triangles).
20%. For higher concentrations, CH4 and alcohols increase the
NH3 laminar flame speed linearly with their concentration, while 3.2 NH3 Oxidation Chemical Kinetic Issues
H2 increases that with an exponential law. A particular efficient As mentioned before, the understanding of NH3 oxidation
way to increase the NH3 laminar flame speed is as follows: Under chemistry and the identification of the fuel NOx route are
O2-enriched environments, SL is promptly increased with O2 crucial to define the a priori system operating conditions.

recently updated the rate constants of H2NO + O2 = HNO +

HO2, for high-pressure conditions (up to 300 bar) and
low–intermediate temperatures (450–925 K). Then, HNO
radicals form NO, outlining an important fuel NO formation
route.
Alternatively, NH2 can also react with NO (DeNOx chemistry)
through a termination and a branching reaction, respectively,
NH2+ NO = N2+H2O and NH2+NO = NNH + OH (blue
pathway), active between 1,100 and 1400 K (Glarborg et al.,
1986; Miller and Bowman, 1989; Miller and Glarborg, 1999).
Laminar flame speed and ignition delay time strongly depend on
the ratio between rate constants of the DeNOx chemistry.
In the following step, NNH decomposes via reaction NNH =
N2+H. This reaction is very important as it releases H radicals to
sustain H2/O2 radical branching mechanisms, while its tunneling
nature and the NNH short lifetime make modeling activities very
complex (Klippenstein et al., 2011). The concurrent reaction
NNH + O=NO + NH has then received a lot of attention as a
further important NO formation route (Konnov and de Ruyck,
2001).
For higher temperatures (>1400 K), the NH2 radicals are
quickly dehydrogenated to NH ones (black pathway), which
can consume NO, while forming N2O (via reaction NH +
NO = N2O + H, recently revised by Klippenstein et al., 2011),
FIGURE 5 | Generic scheme for NH3 oxidation chemistry, NOx formation
or release N radicals, available for the classical Zeldovich
routes, DeNOx, NxHy, and N2O chemistry, and the NO-NO2 loop.
mechanism (orange pathway) (O + N2 = N + NO, N + O2 =
O + NO, N + OH = H + NO) (Drake and Blint, 1991) at high
temperatures (>1600 K). Under high pressures/high
With this aim, over the years, many advancements in the temperatures, it has to be remarked that the NOx formation
comprehension of NH3 oxidation chemistry have been reached tends to reduce as third-body reactions (H + OH + M = H2O, H +
based on experimental and theoretical studies, albeit the O2+M = HO2+M) decrease radical concentration, necessary to
development of reliable and robust kinetic schemes, especially sustain the Zeldovich mechanism (Kobayashi et al., 2019; Valera-
in engine-relevant conditions, still needs some efforts. This is Medina et al., 2019).
mainly due to the reduced availability of experimental data under N2O (green pathway) acts as a reservoir of O radicals as it can
high-pressure/high-temperature conditions. Recently, several decompose via reaction N2O + M = N2+O + M under low
experimental pieces of evidence has been proposed by pressures, enhancing the reaction rate of H2+O=H + OH,
different research groups, while sustaining the development of while for high-pressure or fuel-ultra-lean conditions, this
numerical studies toward more comprehensive schemes. reaction reverts defining an important N2O formation route.
All the mechanisms are explained in the general description of Alternatively, N2O is consumed through N2O + H=N2+OH,
the NH3 oxidation chemistry: In Figure 5 a general scheme of releasing OH radicals for temperatures above 1650 K, while
NH3 oxidation chemistry is provided. decreasing characteristic fuel ignition delay times (Mathieu
NH3 may undergo dehydrogenation reactions to NH2 through et al., 2012).
OH, H, and O radicals or thermal decomposition (dark gray The NO-NO2 loop (purple pathway) boosts the conversion of
pathway). NH2 radicals may recombine to N2Hx species (red unreactive HO2 radicals into reactive OH radicals through the
pathway), especially for fuel-rich/pyrolytic conditions and under reaction NO + HO2 = NO2+OH, thus enhancing the mixture
high-pressure conditions. Konnov and de Ruyck, 2000, have reactivity, while recycling back NO via NO2+H=NO + OH,
introduced the N2Hx route, from N2H4 decomposition together with a further release of OH radicals.
experiments in shock tubes, relevant to fuel-rich conditions, The N2O and NO-NO2 effects on fuel characteristic chemical
defining later also a new NOx formation route through N2H3 times should be carefully evaluated for EGR engines (Mathieu
radicals (Konnov and de Ruyck, 2001). The importance of this et al., 2012; Ahmed et al., 2016), where flue gases are recirculated
pathway for the prediction of NH3 laminar flame velocities, back to the engine to limit the adiabatic flame temperature, while
especially for fuel-rich conditions, has been highlighted by constraining NOx emissions to threshold values.
many authors (Nakamura and Hasegawa, 2017; Okafor et al., Mathieu and Petersen (2015) measured NH3 ignition delay
2018; Otomo et al., 2018; Shrestha et al., 2018; Stagni et al., 2020). time for high pressures (30 bar) and high temperatures in a shock
Alternatively, NH2 radicals can react with HO2 radicals at low tube and highlighted the importance of N2O and NO2 routes.
temperatures or high pressures, forming H2NO (light-gray Ahmed et al. (2016) and Zhang et al. (2017) clarified the NO-NO2
pathway). Song et al. (2016) and Stagni et al. (2020) have interconversion comes through a more complex pathway,

involving intermediate species such as HONO, HNO2, HONO2, reaction H + O2 = OH + O, thus accelerating ignition delay times.
and HNO3. Sabia et al. (2020) and Manna et al. (2022) have performed
Beyond the relatively simple description of NH3 oxidation experiments in a JSFR for NH3/H2 mixtures, providing for
chemistry, any routes here described have been and are actually evidence of a mutual inhibiting interaction among H2 and
constantly discussed and updated on the basis of new NH3, with a plausible role of NH3 as a strong collider in
experimental evidence and theoretical studies. third-body reactions, due to NH3 strong polarity, like water
Given the large number of kinetic schemes developed in the (Michael et al., 2002). This aspect should be carefully
last decade (Glarborg, et al., 1986; Konnov and de Ruyck, 2000; addressed for high-pressure systems, where reaction rate
Skreiberg et al., 2004; Dagaut et al., 2008; Mével et al., 2009; Tian pressure dependence, involving also the NxHy species
et al., 2009; Duynslaegher et al., 2012; Mathieu and Petersen, formation route with many third-body reactions, covers an
2015; Song et al., 2016; Nakamura and Hasegawa, 2017; Zhang important role (Glarborg et al., 2021).
et al., 2017; Otomo et al., 2018; Shrestha et al., 2018; Stagni et al., Rasmussen et al. (2008) and then Dai et al. (2020)
2020), Rocha et al. (2021) performed a numerical study to demonstrated that fuel NO can have a strong sensitizing effect
compare available detailed models against ignition delay times on CH4 ammonia chemistry through the interaction with NO-
from Mathieu and Petersen (2015) and laminar flame data from NO2 species via NO2+CH3 = NO + CH3O and NO + CH3OO =
Hayakawa et al. (2015), Pfahl et al. (2000), and Duynslaegher et al. NO2+CH3O, as well as through the NO-NO2 loop, while
(2012) (up to 5 atm). The claimed main differences among CH4+NH2 = CH3+NH3 contributes substantially to the
mechanisms are related to NOx formation routes, recognizing decomposition of CH4 under fuel-rich conditions.
the reaction HNO + O2 = HO2+NO and the ammonia pyrolysis
for fuel-rich conditions (such as 2NH2 = NH3+NH) as
fundamental steps to predict NO emissions. Nakamura and 4 AMMONIA AS FUEL IN INTERNAL
Hasegawa (2017) and Zhang et al. (2017) have also COMBUSTION ENGINES
demonstrated the importance of thermochemical properties to
predict NH3 weak flames and ignition delay times at high Nowadays, ammonia is considered the most promising solution for
pressures. Kovács et al. (2020) compared 8 detailed kinetic abating GHG emission in large-bore internal combustion engines
mechanisms for NH3 pyrolysis and oxidation with respect to for marine transportation and power generation sector (Kurien
experimental data. The authors noticed a large discrepancy and Mittal, 2022), where the low energy density characteristic of
among model predictions, while warning about the necessity the current battery technologies makes electric propulsion
to extent the validation procedure against a larger NH3 database. unfeasible. Some modifications are necessary to allow internal
From this brief overview of kinetic scheme development over the combustion engines running with NH3. First, when working
recent years, it is clear that NH3 oxidation chemistry along with NO with port fuel injection, an 8-bar fuel tank and a supply system
formation routes still presents many open issues: Large rate constant similar to LPG have to be introduced, generally equipped with a
uncertainties, different thermochemical parameters, the significant heated vaporizer before the injector (Frigo and Gentili, 2013). Due
non-Arrhenius behavior of NH3 dehydrogenation reactions, rate to the growing interest in ammonia, methanol, and other low-
pressure dependence description, especially relevant to high-pressure viscosity fuels, more recent solutions have been developed allowing
conditions, the NH3 pyrolysis chemistry along with the NxHy route, the high-pressure common rail direct injection (Willmann et al., 2021).
tunneling nature of NNH reactions, the strong sensitivity of NO to the In case of spark-ignition engines, an increase in compression ratio
DeNOx chemistry, and the kinetics related to the NO-NO2 loop, to is provided to exploit the high octane number of ammonia and
N2O, and to H2NO/HONO species still have to be properly addressed. compensate for the low laminar flame speed (Garabedian and
Recently, experimental investigations relevant to engines have Johnson, 1966). In order to accelerate the ammonia burning rate,
been realized also for NH3/H2 (He et al., 2019; Chen et al., 2021), few percentages of H2 are generally added and a dissociation
NH3/CH4 (Dai et al., 2020; Xiao et al., 2020; Arunthanayothin catalyst is often employed to generate H2 onboard by ammonia
et al., 2021; Shu et al., 2021), NH3/diesel (Feng et al., 2020), NH3/ cracking (Ryu et al., 2014a). In this case, in spark-ignition engines
n-heptane (Yu et al., 2020), NH3/DEE (Issayev et al., 2021), and the spark plug material is changed to avoid hydrogen backfiring
NH3/CH3OH and C2H5OH (Wang et al., 2021) blends as phenomena (Dimitriou and Javaid, 2020).
strategies to improve the laminar flame speed/ignition delay Even though great attention is paid by the scientific community
times of NH3. and industry, practical applications on internal combustion
The oxidation chemistry of NH3 and fuel “enhancer” has to be engines fueled with ammonia are still limited. This section aims
carefully addressed, since many authors reported a strong at giving an insight into ammonia combustion in both spark- and
chemical interaction. In addition, for complex molecules, compression-ignition engines, highlighting the strengths and
detailed kinetic mechanisms had to be constructed ad hoc by weaknesses of each investigated solution.
simply merging kinetic models; thus, NH3–fuel interaction may
suffer in the absence of chemistry subsets.
For instance, Chen et al. (2021) have characterized H2-NH3 4.1 Ammonia as Fuel in Spark-Ignition
ignition delay times up to 10 atm, demonstrating that the reaction Engines
NH3+H=NH2+H2 reconverts back NH2 radicals to NH3, First attempts of fueling spark-ignition engines with NH3 date
releasing H radicals to sustain the high-temperature branching back to the end of the 60s for military application with the aim of

making vehicles independent of hydrocarbon fuels (Cornelius equivalence ratio, ϕ, for different H2 volume fractions. In agreement
et al., 1966). In the previous study (Garabedian and Johnson, with aforementioned works, the optimal indicated efficiency was
1966), the authors experimentally investigated the effect of reached with low concentrations of hydrogen, between 5% and 20%,
anhydrous ammonia on the performance of a 48 kW and lean near stochiometric condition. A maximum of about 39%
maximum rated power, 4,000 rpm maximum engine speed, was achieved with H2 20%v at ϕ 0.9. Too high hydrogen
and 4-cylinder spark-ignition engine. First tests without any concentrations result in efficiency detriment due to an increase in
modification except an LPG carburetor for ammonia supply wall heat losses, as a consequence of higher flame temperatures.
highlighted a reduction in maximum rated power and engine Alternative or in combination with hydrogen, natural gas is
speed to 7 kW and 2000 rpm, respectively. By adding a few considered a viable way to sustain the NH3 combustion as it was
quantities of hydrogen (between 2% and 4%), an increase in widely used in the recent past as a primary fuel in the large-bore
power output of up to about 20 kW was found, while the speed engine. Therefore, using a blend of natural gas and ammonia
range was extended up to 3,200 rpm. Further improvements were represents a step toward the decarbonization path. Oh et al. (2021)
achieved by increasing the compression ratio thanks to the high tested the influence of ammonia–natural gas blends on the
octane number of NH3, allowing 40 kW power output at performance and exhaust emissions of a heavy-duty, 6-cylinder
4,000 rpm. More recent applications on spark-ignition engines spark-ignition engine designed for compressed natural gas (CNG)
mainly concern the use of ammonia in a blend with a secondary fueling. Experiments were focused on partial load, low-speed
fuel to increase the burning rate, generally H2, CH4 (Chai et al., conditions: The engine was fueled with 50% NH3-50% CNG.
2021), or H2/CH4 (Mashruk et al., 2022). In Lhuillier et al.’s The substitution of CNG with ammonia resulted in a CO2
(2019a) study, the authors tested the performance of a GDI reduction of about 28%, while the charge dilution was limited
single-cylinder engine fueled with gaseous ammonia/air by the detriment in combustion stability involved with low NH3
mixture at a fixed engine speed of 1,500 rpm by varying the burning velocity allowing a maximum equivalence ratio of 1.5.
intake pressure. They demonstrated the feasibility of pure Controversial results were obtained by Lhuillier et al. (2021),
ammonia combustion at wide-open throttle conditions. concerning the effect of methane on the combustion duration
Further improvements in stability were achieved with boosted of ammonia-fueled spark-ignition engines. CH4 volume
pressure, while at partial load, the addition of hydrogen was concentration was varied between 5 and 15% at different
needed to keep the cycle-to-cycle variability under acceptable equivalence ratios, to investigate the potential of CH4 as a
values. At full load, the engine performance with pure ammonia combustion promoter. Methane slightly sped up the combustion
was comparable with the one obtained with methane used as a at the rich mixture condition (ϕ = 1.1), which did not significantly
reference, with an indicated efficiency of about 36%. Based on the influence the combustion duration at the stoichiometric condition,
literature, the need for a combustion enhancer in blend with the while it reduced burning velocity at the lean condition (ϕ = 0.9).
ammonia is apparent to operate the engine over the whole load With the aim of reducing CO2 emissions, ammonia was also used
range. With this aim, hydrogen is the best solution when thinking as secondary fuel in binary/ternary blends with gasoline and
about the engine performance; on the contrary, the issues related alcohol fuels. Due to its high octane number, ammonia allows
to its storage and transportation make this solution unreliable in a advancing spark timing and boosting intake pressure; in this way, it
dual-fuel configuration. As argued by first studies on the NH3 is possible to compensate for the loss in power output linked to the
combustion (Garabedian and Johnson, 1966; Starkman et al., low energy density and burning velocity. In Ryu et al.’s (2014b)
1967), an NH3 dissociation catalyst can provide the necessary study, the potential of NH3 direct injection was explored in a dual-
amount of hydrogen, avoiding to stocking it in a separate tank. fuel gasoline port fuel–injected spark-ignition engine. When
Interestingly, the heat required by ammonia cracking working in a dual-fuel mode, the power output ascribable to
endothermic reactions can be recovered by engine gas exhaust gasoline was kept constant, while the total power was increased
(Comotti and Frigo, 2015). In Lhuillier et al.’s (2019b) study, the by adjusting the ammonia injection. Results were compared with
authors investigated the influence of hydrogen addition on the pure gasoline operation at the same load, highlighting similar
performance and emissions of an ammonia-fueled SI engine. The overall brake-specific energy consumption. On the contrary,
H2 volume content varied from 5% to 15% at different equivalent NOx emissions were strongly penalized. Haputhanthri et al.
ratios and intake pressures. The use of hydrogen as a combustion (2014) explored the potential of ethanol and methanol to
enhancer allowed acceptable combustion stability over the whole increase the ammonia solubility in gasoline and hence improve
engine map. 10% H2 concentration was found as the optimum to its content in ternary blends. They found an increase in ammonia
increase combustion efficiency without compromising exhaust content from 3.7%v in the case of binary NH3/gasoline blends to
emissions. The best efficiency results were achieved at lean near 30%v in ternary blends with 30%v of methanol. Independent of
stoichiometric conditions. Further charge dilution results in a percentage composition, at high engine speed, introducing
significant increase in NOx and NH3 at the exhaust without ammonia in alcohol/gasoline blends resulted in a torque increase.
combustion efficiency improvements. Similar findings were
highlighted in Frigo and Gentili (2013).
Lhuillier et al. (2020a) performed an extensive investigation on 4.2 Ammonia as Fuel in Compression-
the use of NH3/H2 blends with different equivalence ratios and H2 Ignition Engines
volume concentrations up to 60% in a single-cylinder spark-ignition Combustion of ammonia in compression-ignition engines is
engine. Figure 6 shows the indicated efficiency as a function of challenging due to its very low reactivity, which makes it more

FIGURE 6 | Indicated efficiency as a function of equivalence ratio ϕ under different hydrogen concentrations (Lhuillier et al., 2020b).
attractive for positive ignition. On the contrary, the recent interest maximum. Further improvements in combustion efficiency
in ammonia as fuel is mainly pushed by the marine shipping can be achieved by directly injecting ammonia in a
industry, which prominently runs with compression-ignition combustion chamber at high pressure. Li et al. (2022)
large-bore engines. In light of this, several solutions are under compared the combustion characteristics and exhaust
investigation to burn ammonia, either in pure or in dual-fuel emissions of a dual-fuel diesel engine with those of two
mode, in compression-ignition engines. First studies on the use of different ammonia injection systems: indirect low-pressure and
ammonia in diesel engines date back to the end of the 60s on direct high-pressure one. Results highlighted an increase in
behalf of the US Army Energy Depot program. In 1967, Gray et al. maximum energy replacement when switching from the low-
(1967) burned pure ammonia in a Cooperative Fuel Research to high-pressure injection system from 80% up to 97%. The low-
(CFR) engine, increasing the compression ratio up to 35:1 and pressure dual-fuel mode provided a higher indicated thermal
intake temperature to 423 K. The low reactivity of ammonia efficiency, while high-pressure dual-fuel mode limited the
combined with the high compression ratio resulted in a pressure unburned NH3 exhaust emissions.
peak of about 150 bar, likely due to a homogeneous charge Several applications have been explored in the use of NH3 in
combustion process. Introducing diesel fuel pilot as an ignition combination with alternative fuels in compression-ignition
trigger allowed a reduction in compression to 15.2:1. Similar engines. Reiter and Kong (2008) investigated the effect of
results can be found in the literature of the same age (Pearsall and soybean oil methyl ester as a combustion trigger for ammonia.
Garabedian, 1968), suggesting the use of dual-fuel mode Replacing biodiesel with diesel did not result in significant
combustion. Therefore, more recent studies aimed to optimize performance and emission variations. Tay et al. (2017)
the performance and exhaust emissions of NH3/diesel-fueled performed a numerical study on the use of kerosene in the
engines to reduce GHG emissions without penalizing the mixture or as an alternative to diesel for triggering the
performance. Yousefi et al. (2022) investigated the effect of combustion of NH3. They found an advance in the start of
ammonia/diesel ratio and diesel injection strategy on the ignition when switching from diesel to kerosene, resulting in a
behavior of a single-cylinder, heavy-duty common rail dual- more complete combustion of NH3 in the regions close to
fuel engine. Ammonia energy fraction was regulated through a cylinder liner and crevices. Some attempts have been
port fuel injection. The reduction in the diffusive diesel performed to inject dimethyl ether (DME)/NH3 mixtures as
combustion stage due to the introduction of premixed air/NH3 NH3 is miscible with DME. In Ryu et al.’s (2014c) study, pure
charge results in a lower in-cylinder pressure peak, prolonging the DME and two different DME/NH3 mixtures (40% and 60%w of
combustion duration. Consequently, a reduction in NOx up to NH3) were directly injected into a compression-ignition engine.
58% is achieved with the maximum NH3 energy fraction of 40%. The authors found a worsening of performance with higher cyclic
Diesel injection strategy optimization allows keeping ITE almost variability by increasing NH3%. Moreover, the combustion
constant with a reduction in GHG of about 12%. As prolongation and lower temperature of NH3 combustion
demonstrated by Reiter and Kong (2008), NH3 can be used as resulted in higher CO and HC emissions.
a primary fuel in turbocharged diesel engines with few NH3 can be successfully used as a hydrogen carrier thanks to
modifications to the intake port. Tests were performed at the reliability of onboard systems for hydrogen production by
different engine loads and speeds. An ammonia energy means of NH3 cracking or dissociation (Kurien and Mittal, 2022).
fraction of 95% was achieved with engine torque close to Gill et al. (2012) performed an experimental analysis of the

FIGURE 7 | Brake thermal efficiency for different intake air additives: gaseous ammonia, pure hydrogen, and dissociated ammonia (Gill et al., 2012).
influence of dissociated NH3 on the combustion and emission of available conversion systems, with main concerns in its
the direct-injection diesel engine. With this aim, the 3%v of intake application in the internal combustion engine.
air was replaced with gaseous ammonia, dissociated ammonia, Nevertheless, the potential impact of its use as a energy carrier
and pure hydrogen. Figure 7 shows the effect of the dual-fuel on decarbonization has catalyzed the attention of academic and
operation on the brake thermal efficiency and CO2 emissions. industrial research on studying and testing possible solutions to
Both ammonia and hydrogen provide a reduction in combustion overcome disadvantages, from its green production to its
efficiency compared with pure diesel fueling. This trend can be effective use.
explained by combustion mechanisms of H2 and NH3 compared Ammonia will only make sense as a green fuel if the routes for
with diesel. In fact, the dilute mixture conditions, typical of its production turn green. Currently, at an industrial level,
compression-ignition engines, penalize the premixed flame ammonia is produced using nitrogen and hydrogen in the gas
propagation worsening the combustion efficiency. Replacing phase through the Haber–Bosch (H-B) process. From an
3%v of intake air with carbon-free NH3 or H2 allows reducing environmental point of view, this path is too energy-intensive
diesel amount by about 15% with benefits on CO2 emission up to and unsustainable: The H-B process is mainly based on fossil fuels
about 12%. as an energy source and as a raw material since almost all of the
hydrogen gases used for ammonia synthesis are produced by
steam reforming of natural gas. In this review, two different
5 CONCLUSION pathways for producing green ammonia were evaluated: The first,
of considerable long-term scope, is based on the H-B process
The need for immediate solutions to reduce greenhouse gas fueled with hydrogen from renewable sources (green hydrogen),
emissions represents one of the most serious challenges for the and the whole process is powered by electricity from completely
transport sector since the internal combustion engine invention. renewable sources. The conversion of traditional synthesis plants
Despite the run to the electrification, the route from combustion from steam reforming feed to green hydrogen feed (e.g., by
to electric propulsion is long and several issues have to be integrating water electrolysis into the process) requires plant
addressed before reaching this goal. Furthermore, electric design flexibility and optimal allocation of energy sources; and
propulsion cannot replace internal combustion engines, even the second path is based on the electrochemical synthesis of
though they are competing with each other. In this scenario, ammonia; in this case, the H-B process is no longer necessary:
green ammonia is considered a promising fuel as it is carbon-free, The processes connected to this second path are currently at TRL
it has a relatively high-volume energy density, and it is easy to 1, and further research and development activities would be
store and transport. required before being able to consider large-scale industrial
There are several drawbacks, in terms of safety and efficiency, production.
that have limited the deployment of ammonia on a large scale in Much attention has been dedicated to NH3 as fuel, with the
the past due to its chemical–physical characteristics. Indeed, development and optimization of many detailed kinetic schemes.
toxicity and poor combustion properties limit ammonia Their availability is mandatory for designing and optimizing
utilization as a direct substitute for standard fuels in the thermal conversion systems where ammonia is used, as well as

for setting up their digital twins. Most of these schemes were who look at ammonia since it may be burnt by existing engine
derived from mechanisms conceived for NOx formation/ architecture with retrofitting modifications. The high
reduction, at low pressures (through prompt, fuel, and thermal autoignition temperature and the low burning velocity impose
NO routes), and thermal De-NOx, and have been updated on the the use of combustion promoters in order to limit flame
basis of recent experimental evidence, while at only recently high- quenching and misfiring. The most convincing solution to this
pressure/high-temperature conditions, relevant to ICEs, issue is considered onboard production of H2 from NH3 cracking,
experimental data have been proposed, thus boosting a further recovering engine out heat to support endothermic reactions.
development in an attempt to provide for reliable and robust Experimental tests on spark-ignition engines demonstrate that
kinetic schemes. However, NH3 oxidation chemistry presents still H2-added NH3 combustion can replace CH4 without efficiency
many open issues, mainly related to large rate constant losses. Further improvements are expected with the development
uncertainties, different thermochemical parameters, and rate of high-pressure direct-injection systems, which avoid NH3 slip
pressure dependence description, relevant to high-pressure and increase combustion stability. Interest is also paid to the
conditions. In addition, some critical steps, such as the NH3 combustion of ammonia in compression-ignition engines since it
pyrolysis chemistry along with the NxHy route, the tunneling should limit modifications to existing ship engine architectures.
nature of NNH reactions, and the strong sensitivity of NH3 to the On the contrary, this solution results in a too high detriment of
DeNOx chemistry, to the NO-NO2 loop, and to N2O and H2NO/ efficiency since the low reactivity of NH3 implies a change in the
HONO species, still have to be properly addressed. These issues combustion mechanism, which is predominantly premixed,
are stressed in case of addition of fuel enhancers, where a direct compromising the thermal efficiency. The increase in injection
coupling between ammonia–ammonia radicals and fuel pressure of modern common rail systems for low-viscosity fuels
oxidation chemistry has to be taken into account. Recently, could lead the way to a new generation of compression-ignition
many efforts have been done in virtue of the availability of engines allowing diesel similar to the combustion of ammonia.
new data at high pressure/high temperature, in the form of
laminar flame speeds and autoignition delay times as
fundamental parameters to predict for ICE conditions and a AUTHOR CONTRIBUTIONS
set of detailed kinetic models to be used for the evaluation of
combustion parameters are available, along with reduced CT and MJ conceptualized the study, investigated the study,
schemes for CFD purposes. wrote the original draft, and wrote, reviewed, and edited the
Practical applications of ammonia in internal combustion manuscript. LM and PS conceptualized the study, investigated the
engines are attracting the interest from shipping stakeholders study, and wrote the original draft.
Titania and Other Metal Oxides. J. Photochem. Photobiol. A Chem. 88 (1),

REFERENCES 53–64. doi:10.1016/1010-6030(94)03994-6
Cai, X., Fu, C., Iriawan, H., Yang, F., Wu, A., Luo, L., et al. (2021). Lithium-
Agrawal, R., and Woodward, D. W. (1991). Efficient Cryogenic Nitrogen mediated Electrochemical Nitrogen Reduction: Mechanistic Insights to
Generators: An Exergy Analysis. Gas Sep. Purif. 5 (3), 139–150. doi:10.1016/ Enhance Performance. iScience 24 (10), 103105. doi:10.1016/j.isci.2021.
0950-4214(91)80012-t 103105
Ahmed, S. F., Santner, J., Dryer, F. L., Padak, B., and Farouk, T. I. (2016). Capurso, T., Stefanizzi, M., Torresi, M., and Camporeale, S. M. (2022). Perspective
Computational Study of NOx Formation at Conditions Relevant to Gas of the Role of Hydrogen in the 21st Century Energy Transition. Energy Convers.
Turbine Operation, Part 2: NOx in High Hydrogen Content Fuel Manag. 251, 114898. doi:10.1016/j.enconman.2021.114898
Combustion at Elevated Pressure. Energy fuels. 30 (9), 7691–7703. doi:10. Chai, W. S., Bao, Y., Jin, P., Tang, G., and Zhou, L. (2021). A Review on Ammonia,
1021/acs.energyfuels.6b00421 Ammonia-Hydrogen and Ammonia-Methane Fuels. Renew. Sustain. Energy
Ariemma, G. B., Sorrentino, G., Ragucci, R., de Joannon, M., and Sabia, P. (2022). Rev. 147, 111254. doi:10.1016/j.rser.2021.111254
Ammonia/Methane Combustion: Stability and NOx Emissions. Combust. Chehade, G., and Dincer, I. (2021). Progress in Green Ammonia Production as
Flame 241, 112071. doi:10.1016/j.combustflame.2022.112071 Potential Carbon-free Fuel. Fuel 299, 120845. doi:10.1016/j.fuel.2021.120845
Arunthanayothin, S., Stagni, A., Song, Y., Herbinet, O., Faravelli, T., and Battin- Chen, H., Dong, F., and Minteer, S. D. (2020). The Progress and Outlook of
Leclerc, F. (2021). Ammonia-methane Interaction in Jet-Stirred and Flow Bioelectrocatalysis for the Production of Chemicals, Fuels and Materials. Nat.
Reactors: An Experimental and Kinetic Modeling Study. Proc. Combust. Catal. 3, 225–244. doi:10.1038/s41929-019-0408-2
Inst. 38 (1), 345–353. doi:10.1016/j.proci.2020.07.061 Chen, J., Jiang, X., Qin, X., and Huang, Z. (2021). Effect of Hydrogen Blending on
Ashik, U. P. M., Viswan, A., Kudo, S., and Hayashi, J.-i. (2018). “Nanomaterials as the High Temperature Auto-Ignition of Ammonia at Elevated Pressure. Fuel
Catalysts,” in Micro and Nano Technologies, Applications of Nanomaterials. 287, 119563. doi:10.1016/j.fuel.2020.119563
Editors S. M. Bhagyaraj, O. S. Oluwafemi, N. Kalarikkal, and S. Thomas, 45–82. Choe, J., Sun, W., Ombrello, T., and Carter, C. (2021). Plasma Assisted Ammonia
doi:10.1016/B978-0-08-101971-9.00003-X Combustion: Simultaneous NOx Reduction and Flame Enhancement.
Bicer, Y., and Dincer, I. (2017). Assessment of a Sustainable Electrochemical Combust. Flame 228, 430–432. doi:10.1016/j.combustflame.2021.02.016
Ammonia Production System Using Photoelectrochemically Produced Comotti, M., and Frigo, S. (2015). Hydrogen Generation System for Ammonia-
Hydrogen under Concentrated Sunlight. ACS Sustain. Chem. Eng. 5 (9), Hydrogen Fuelled Internal Combustion Engines. Int. J. Hydrogen Energy 40
8035–8043. doi:10.1021/acssuschemeng.7b01638 (33), 10673–10686. doi:10.1016/j.ijhydene.2015.06.080
IEA Bioenergy,Binder, M., Kraussler, M., Kuba, M., and Luisser, M. (2018). Hydrogen Cornelius, W., Huellmantel, L. W., and Mitchell, H. R. (1966). Ammonia as an
from Biomass Gasification. https://www.ieabioenergy.com/wp-content/uploads/ Engine Fuel. SAE Trans. 74, 300–326.
2019/01/Wasserstoffstudie_IEA-final.pdf (Accessed May 15, 2022). Dagaut, P., Glarborg, P., and Alzueta, M. (2008). The Oxidation of Hydrogen
Boucher, D. L., Davies, J. A., Edwards, J. G., and Mennad, A. (1995). An Cyanide and Related Chemistry. Prog. Energy Combust. Sci. 34 (1), 1–46. doi:10.
Investigation of the Putative Photosynthesis of Ammonia on Iron-Doped 1016/j.pecs.2007.02.004

Dai, L., Gersen, S., Glarborg, P., Mokhov, A., and Levinsky, H. (2020). Autoignition IRENA - International Renewable Energy Agency (2020). Green Hydrogen Cost
Studies of NH3/CH4 Mixtures at High Pressure. Combust. Flame 218, 19–26. Reduction: Scaling up Electrolysers to Meet the 1.5⁰C Climate Goal. https://irena.
doi:10.1016/j.combustflame.2020.04.020 org/-/media/Files/IRENA/Agency/Publication/2020/Dec/IRENA_Green_hydrogen_
Dimitriou, P., and Javaid, R. (2020). A Review of Ammonia as a Compression cost_2020.pdf (Accessed May 15, 2022).
Ignition Engine Fuel. Int. J. Hydrogen Energy 45 (11), 7098–7118. doi:10.1016/j. Issayev, G., Giri, B. R., Elbaz, A. M., Shrestha, K. P., Mauss, F., Roberts, W. L., et al.
ijhydene.2019.12.209 (2021). Combustion Behavior of Ammonia Blended with Diethyl Ether. Proc.
Drake, M. C., and Blint, R. J. (1991). Calculations of NOx Formation Pathways in Combust. Inst. 38 (1), 499–506. doi:10.1016/j.proci.2020.06.337
Propagating Laminar, High Pressure Premixed CH4/air Flames. Combust. Sci. Jabbour, T., and Clodic, D. F. (2004). Burning Velocity and Refrigerant
Technol. 75 (4-6), 261–285. doi:10.1080/00102209108924092 Flammability Classification/DISCUSSION. ASHRAE Trans. 110, 522.
Duynslaegher, C., Contino, F., Vandooren, J., and Jeanmart, H. (2012). Modeling of Klippenstein, S. J., Harding, L. B., Glarborg, P., and Miller, J. A. (2011). The Role of
Ammonia Combustion at Low Pressure. Combust. Flame 159 (9), 2799–2805. NNH in NO Formation and Control. Combust. Flame 158 (4), 774–789. doi:10.
doi:10.1016/j.combustflame.2012.06.003 1016/j.combustflame.2010.12.013
European Commission (2021). Opening Keynote by the President: European Kobayashi, H., Hayakawa, A., Somarathne, K. D. K. A., and Okafor, E. C. (2019).
Hydrogen Week. Available at https://ec.europa.eu/commission/presscorner/ Science and Technology of Ammonia Combustion. Proc. Combust. Inst. 37 (1),
detail/en/speech_21_6421 (Accessed May 15, 2022). 109–133. doi:10.1016/j.proci.2018.09.029
Feng, Y., Zhu, J., Mao, Y., Raza, M., Qian, Y., Yu, L., et al. (2020). Low-temperature Konnov, A. A., and de Ruyck, J. (2001). Temperature-dependent Rate Constant for
Auto-Ignition Characteristics of NH3/diesel Binary Fuel: Ignition Delay Time the Reaction NNH + O → NH + NO. Combust. Flame 125 (4), 1258–1264.
Measurement and Kinetic Analysis. Fuel 281, 118761. doi:10.1016/j.fuel.2020. doi:10.1016/s0010-2180(01)00250-4
118761 Konnov, A. A., and Ruyck, J. D. (2001). A Possible New Route for No Formation
Frigo, S., and Gentili, R. (2013). Analysis of the Behaviour of a 4-stroke Si Engine Vian2h3. Combust. Sci. Technol. 168 (1), 1–46. doi:10.1080/
Fuelled with Ammonia and Hydrogen. Int. J. Hydrogen Energy 38 (3), 00102200108907830
1607–1615. doi:10.1016/j.ijhydene.2012.10.114 Konnov, A. A., and Ruyck, J. D. (2000). Kinetic Modeling of the Thermal
Garabedian, C. G., and Johnson, J. H. (1966). The Theory of Operation of an Decomposition of Ammonia. Combust. Sci. Technol. 152 (1), 23–37. doi:10.
Ammonia-Burning Internal Combustion Engine. USCFSTI, AD 1080/00102200008952125
Rep. (United States) 41 (15). Kovács, M., Papp, M., Zsély, I. G., and Turányi, T. (2020). Determination of Rate
Gardiner, M., and Satyapal, S. (2009). Energy Requirements for Hydrogen Gas Compression Parameters of Key N/H/O Elementary Reactions Based on H2/O2/NOx
and Liquefaction as Related to Vehicle Storage Needs DOE Hydrogen and Fuel Cells Combustion Experiments. Fuel 264, 116720.
Program Record. Available online: https://www.hydrogen.energy.gov/pdfs/ Kurien, C., and Mittal, M. (2022). Review on the Production and Utilization of
9013_energy_requirements_for_hydrogen_gas_compression.pdf (accessed on June Green Ammonia as an Alternate Fuel in Dual-Fuel Compression Ignition
13, 2019). Engines. Energy Convers. Manag. 251, 114990. doi:10.1016/j.enconman.2021.
Ghassan, C., and Ibrahim, D. (2020). A Novel Method for a New Electromagnetic- 114990
Induced Ammonia Synthesizer. Int. J. Energy Res. 44 (9), 7183–7197. doi:10. Lamb, K. E., Viano, D. M., Langley, M. J., Hla, S. S., and Dolan, M. D. (2018). High-
1002/er.v44.910.1002/er.5355 Purity H2 Produced from NH3 via a Ruthenium-Based Decomposition Catalyst
Gill, S. S., Chatha, G. S., Tsolakis, A., Golunski, S. E., and York, A. P. E. (2012). and Vanadium-Based Membrane. Ind. Eng. Chem. Res. 57 (23), 7811–7816.
Assessing the Effects of Partially Decarbonising a Diesel Engine by Co-fuelling doi:10.1021/acs.iecr.8b01476
with Dissociated Ammonia. Int. J. hydrogen energy 37 (7), 6074–6083. doi:10. Lhuillier, C., Brequigny, P., Contino, F., and Mounaïm-Rousselle, C. (2019a).
1016/j.ijhydene.2011.12.137 “Combustion Characteristics of Ammonia in a Modern Spark-Ignition Engine,”
Glarborg, P., Hashemi, H., Cheskis, S., and Jasper, A. W. (2021). On the Rate in Conference on Sustainable Mobility. doi:10.4271/2019-24-0237
Constant for NH2+HO2 and Third-Body Collision Efficiencies for Lhuillier, C., Brequigny, P., Contino, F., and Mounaïm-Rousselle, C. (2021).
NH2+H(+M) and NH2+NH2(+M). J. Phys. Chem. A 125 (7), 1505–1516. Experimental Investigation on Ammonia Combustion Behavior in a Spark-
doi:10.1021/acs.jpca.0c11011 Ignition Engine by Means of Laminar and Turbulent Expanding Flames. Proc.
Glarborg, P., Miller, J. A., and Kee, R. J. (1986). Kinetic Modeling and Sensitivity Combust. Inst. 38 (4), 5859–5868. doi:10.1016/j.proci.2020.08.058
Analysis of Nitrogen Oxide Formation in Well-Stirred Reactors. Combust. Lhuillier, C., Brequigny, P., Contino, F., and Mounaïm-Rousselle, C. (2020a).
flame 65 (2), 177–202. doi:10.1016/0010-2180(86)90018-0 Experimental Study on Ammonia/hydrogen/air Combustion in Spark Ignition
Gray, J. T., Jr, Dimitroff, E., Meckel, N. T., and Quillian, R. D., Jr (1967). Ammonia Engine Conditions. Fuel 269, 117448. doi:10.1016/j.fuel.2020.117448
Fuel—Engine Compatibility and Combustion. SAE Trans. 75, 785–807. Lhuillier, C., Brequigny, P., Contino, F., and Mounaïm-Rousselle, C. (2019b).
Han, D., Liu, Y., and Huang, Z. (2022). “The Use of Ammonia as a Fuel for “Performance and Emissions of an Ammonia-Fueled SI Engine with Hydrogen
Combustion Engines,” in Engines and Fuels for Future Transport. Energy, Enrichment,” in 14th International Conference on Engines & Vehicles. doi:10.
Environment, and Sustainability. Editors G. Kalghatgi, A. K. Agarwal, F. Leach, 4271/2019-24-0137
and K. Senecal (Singapore: Springer), 233–256. doi:10.1007/978-981-16- Lhuillier, C., Brequigny, P., Lamoureux, N., Contino, F., and Mounaïm-Rousselle,
8717-4_10 C. (2020b). Experimental Investigation on Laminar Burning Velocities of
Han, X., Wang, Z., Costa, M., Sun, Z., He, Y., and Cen, K. (2019). Experimental and Ammonia/hydrogen/air Mixtures at Elevated Temperatures. Fuel 263,
Kinetic Modeling Study of Laminar Burning Velocities of NH3/air, NH3/H2/ 116653. doi:10.1016/j.fuel.2019.116653
air, NH3/CO/air and NH3/CH4/air Premixed Flames. Combust. Flame 206, Li, J., Huang, H., Kobayashi, N., He, Z., and Nagai, Y. (2014). Study on Using
214–226. doi:10.1016/j.combustflame.2019.05.003 Hydrogen and Ammonia as Fuels: Combustion Characteristics and
Haputhanthri, S. O., Maxwell, T. T., Fleming, J., and Austin, C. (2014). Ammonia NOxformation. Int. J. Energy Res. 38 (9), 1214–1223. doi:10.1002/er.3141
Gasoline-Ethanol/methanol Tertiary Fuel Blends as an Alternate Automotive Li, T., Zhou, X., Wang, N., Wang, X., Chen, R., Li, S., et al. (2022). A Comparison
Fuel. ASME Int. Mech. Eng. Congr. Expo. 46514, V06AT07A071. doi:10.1115/ between Low- and High-Pressure Injection Dual-Fuel Modes of Diesel-Pilot-
imece2014-38026 Ignition Ammonia Combustion Engines. J. Energy Inst. 102, 362–373. doi:10.
Hayakawa, A., Goto, T., Mimoto, R., Arakawa, Y., Kudo, T., and Kobayashi, H. 1016/j.joei.2022.04.009
(2015). Laminar Burning Velocity and Markstein Length of Ammonia/air Long, J., Chen, S., Zhang, Y., Guo, C., Fu, X., Deng, D., et al. (2020). Direct
Premixed Flames at Various Pressures. Fuel 159, 98–106. doi:10.1016/j.fuel. Electrochemical Ammonia Synthesis from Nitric Oxide. Angew. Chem. Int. Ed.
2015.06.070 59 (24), 9711–9718. doi:10.1002/anie.202002337
He, X., Shu, B., Nascimento, D., Moshammer, K., Costa, M., and Fernandes, R. X. Lubrano Lavadera, M., Han, X., and Konnov, A. A. (2020). Comparative Effect of
(2019). Auto-ignition Kinetics of Ammonia and Ammonia/hydrogen Mixtures Ammonia Addition on the Laminar Burning Velocities of Methane,
at Intermediate Temperatures and High Pressures. Combust. Flame 206, N-Heptane, and Iso-Octane. Energy fuels. 35 (9), 7156–7168. doi:10.1021/
189–200. doi:10.1016/j.combustflame.2019.04.050 acs.energyfuels.0c03424

MacFarlane, D. R., Cherepanov, P. V., Choi, J., Suryanto, B. H. R., Hodgetts, R. Y., for Ammonia/air and Ammonia/hydrogen/air Combustion. Int. J. Hydrogen
Bakker, J. M., et al. (2020). A Roadmap to the Ammonia Economy. Joule 4 (6), Energy 43 (5), 3004–3014. doi:10.1016/j.ijhydene.2017.12.066
1186–1205. doi:10.1016/j.joule.2020.04.004 Pearsall, T. J., and Garabedian, C. G. (1968). Combustion of Anhydrous Ammonia
Mallick, D., Sharma, S. D., Kushwaha, A., Brahma, H. S., Nath, R., and Bhowmik, R. in Diesel Engines. SAE Trans. 76, 3213–3221.
(2022). “Emerging Commercial Opportunities for Conversion of Waste to Pfahl, U. J., Ross, M. C., Shepherd, J. E., Pasamehmetoglu, K. O., and Unal, C.
Energy: Aspect of Gasification Technology,” in Waste-to-Energy Approaches (2000). Flammability Limits, Ignition Energy, and Flame Speeds in
towards Zero Waste. Editors C. M. Hussain, S. Singh, and L. Goswami, 105–127. H2–CH4–NH3–N2O–O2–N2 Mixtures. Combust. flame 123 (1-2), 140–158.
doi:10.1016/B978-0-323-85387-3.00012-4 doi:10.1016/s0010-2180(00)00152-8
Mallouppas, G., Ioannou, C., and Yfantis, E. A. (2022). A Review of the Latest Piazzi, S., Patuzzi, F., and Baratieri, M. (2022). Energy and Exergy Analysis of
Trends in the Use of Green Ammonia as an Energy Carrier in Maritime Different Biomass Gasification Coupled to Fischer-Tropsch Synthesis
Industry. Energies 15, 1453. doi:10.3390/en15041453 Configurations. Energy 249, 123642. doi:10.1016/j.energy.2022.123642
Manna, M. V., Sabia, P., Sorrentino, G., Viola, T., Ragucci, R., and de Joannon, M. Rasmussen, C. L., Rasmussen, A. E., and Glarborg, P. (2008). Sensitizing Effects of
(2022). New Insight into NH-H2 Mutual Inhibiting Effects and Dynamic NOx on CH4 Oxidation at High Pressure. Combust. Flame 154 (3), 529–545.
Regimes at Low-Intermediate Temperatures. Combust. Flame, 111957. doi:10.1016/j.combustflame.2008.01.012
doi:10.1016/j.combustflame.2021.111957 Reiter, A. J., and Kong, S.-C. (2008). Demonstration of Compression-Ignition
Martín, A. J., Shinagawa, T., and Pérez-Ramírez, J. (2019). Electrocatalytic Engine Combustion Using Ammonia in Reducing Greenhouse Gas Emissions.
Reduction of Nitrogen: from Haber-Bosch to Ammonia Artificial Leaf. Energy fuels. 22 (5), 2963–2971. doi:10.1021/ef800140f
Chem 5 (2), 263–283. doi:10.1016/j.chempr.2018.10.010 Rocha, R. C., Costa, M., and Bai, X.-S. (2021). Combustion and Emission
Mashruk, S., Vigueras-Zuniga, M. O., Tejeda-del-Cueto, M. E., Xiao, H., Yu, C., Characteristics of Ammonia under Conditions Relevant to Modern Gas
Maas, U., et al. (2022). Combustion Features of CH4/NH3/H2 Ternary Blends. Turbines. Combust. Sci. Technol. 193 (14), 2514–2533. doi:10.1080/
Int. J. Hydrogen Energy. doi:10.1016/j.ijhydene.2022.03.254 00102202.2020.1748018
Mathieu, O., Levacque, A., and Petersen, E. L. (2012). Effects of N2O Addition on Ronney, P. D., and Wachman, H. Y. (1985). Effect of Gravity on Laminar Premixed
the Ignition of H2-O2 Mixtures: Experimental and Detailed Kinetic Modeling Gas Combustion I: Flammability Limits and Burning Velocities. Combust.
Study. Int. J. hydrogen energy 37 (20), 15393–15405. doi:10.1016/j.ijhydene. Flame 62 (2), 107–119. doi:10.1016/0010-2180(85)90139-7
2012.07.071 Rossetti (2020). “Reactor Design, Modelling and Process Intensification for
Mathieu, O., and Petersen, E. L. (2015). Experimental and Modeling Study on Ammonia Synthesis,” in Sustainable Ammonia Production. Green Energy
the High-Temperature Oxidation of Ammonia and Related NOx and Technology. Editors Inamuddin, R. Boddula, and A. Asiri (Cham:
Chemistry. Combust. Flame 162 (3), 554–570. doi:10.1016/j. Springer), 17–48. doi:10.1007/978-3-030-35106-9_2
combustflame.2014.08.022 Rouwenhorst, K. H. R., Krzywda, P. M., Benes, N. E., Mul, G., and Lefferts, L.
Mei, B., Zhang, X., Ma, S., Cui, M., Guo, H., Cao, Z., et al. (2019). Experimental and (2021). “Ammonia Production Technologies,” in Techno-Economic Challenges
Kinetic Modeling Investigation on the Laminar Flame Propagation of of Green Ammonia as an Energy Vector. Editors A. Valera-Medina and
Ammonia under Oxygen Enrichment and Elevated Pressure Conditions. R. Banares-Alcantara (Academic Press), 41–83. doi:10.1016/B978-0-12-
Combust. Flame 210, 236–246. doi:10.1016/j.combustflame.2019.08.033 820560-0.00004-7
Mével, R., Javoy, S., Lafosse, F., Chaumeix, N., Dupré, G., and Paillard, C. E. (2009). Ryu, K., Zacharakis-Jutz, G. E., and Kong, S.-C. (2014a). Effects of Gaseous
Hydrogen–nitrous Oxide Delay Times: Shock Tube Experimental Study and Ammonia Direct Injection on Performance Characteristics of a Spark-
Kinetic Modelling. Proc. Combust. Inst. 32 (1), 359–366. Ignition Engine. Appl. energy 116, 206–215. doi:10.1016/j.apenergy.2013.11.067
Michael, J. V., Su, M.-C., Sutherland, J. W., Carroll, J. J., and Wagner, A. F. (2002). Ryu, K., Zacharakis-Jutz, G. E., and Kong, S.-C. (2014c). Performance
Rate Constants for H + O2 + M → HO2 + M in Seven Bath Gases. J. Phys. Chem. Characteristics of Compression-Ignition Engine Using High Concentration
A 106 (21), 5297–5313. doi:10.1021/jp020229w of Ammonia Mixed with Dimethyl Ether. Appl. energy 113, 488–499. doi:10.
Miller, J. A., and Bowman, C. T. (1989). Mechanism and Modeling of Nitrogen 1016/j.apenergy.2013.07.065
Chemistry in Combustion. Prog. energy Combust. Sci. 15 (4), 287–338. doi:10. Ryu, K., Zacharakis-Jutz, G. E., and Kong, S.-C. (2014b). Performance
1016/0360-1285(89)90017-8 Enhancement of Ammonia-Fueled Engine by Using Dissociation Catalyst
Miller, J. A., and Glarborg, P. (1999). Modeling the Thermal De-NOx Process: for Hydrogen Generation. Int. J. hydrogen energy 39 (5), 2390–2398. doi:10.
Closing in on a Final Solution. Int. J. Chem. Kinet. 31 (11), 757–765. doi:10. 1016/j.ijhydene.2013.11.098
1002/(sici)1097-4601(1999)31:11<757::aid-jck1>3.0.co;2-v Sabia, P., Manna, M. V., Ragucci, R., and de Joannon, M. (2020). Mutual Inhibition
Nakamura, H., and Hasegawa, S. (2017). Combustion and Ignition Characteristics Effect of Hydrogen and Ammonia in Oxidation Processes and the Role of
of Ammonia/air Mixtures in a Micro Flow Reactor with a Controlled Ammonia as "strong" Collider in Third-Molecular Reactions. Int. J. Hydrogen
Temperature Profile. Proc. Combust. Inst. 36 (3), 4217–4226. doi:10.1016/j. Energy 45 (56), 32113–32127. doi:10.1016/j.ijhydene.2020.08.218
proci.2016.06.153 Sánchez, A., and Martín, M. (2018). Scale up and Scale Down Issues of Renewable
New Jersey Department of Health (2016). Hazardous Substance Fact Ammonia Plants: Towards Modular Design. Sustain. Prod. Consum. 16,
Sheet – Ammonia. https://nj.gov/health/eoh/rtkweb/documents/fs/0084.pdf 176–192. doi:10.1016/j.spc.2018.08.001
(Accessed May 15, 2022). Shen, H., Choi, C., Masa, J., Li, X., Qiu, J., Jung, Y., et al. (2021). Electrochemical
Oh, S., Park, C., Kim, S., Kim, Y., Choi, Y., and Kim, C. (2021). Natural Gas- Ammonia Synthesis: Mechanistic Understanding and Catalyst Design. Chem 7
Ammonia Dual-Fuel Combustion in Spark-Ignited Engine with Various Air- (7), 1708–1754. doi:10.1016/j.chempr.2021.01.009
Fuel Ratios and Split Ratios of Ammonia under Part Load Condition. Fuel 290, Shiva Kumar, S., and Himabindu, V. (2019). Hydrogen Production by PEM Water
120095. doi:10.1016/j.fuel.2020.120095 Electrolysis - A Review. Mater. Sci. Energy Technol. 2 (3), 442–454. doi:10.1016/
Okafor, E. C., Kurata, O., Yamashita, H., Inoue, T., Tsujimura, T., Iki, N., j.mset.2019.03.002
Hayakawa, A., Ito, S., Uchida, M., and Kobayashi, H. (2021). Liquid Shrestha, K. P., Seidel, L., Zeuch, T., and Mauss, F. (2018). Detailed Kinetic
Ammonia Spray Combustion in Two-Stage Micro Gas Turbine Combustors Mechanism for the Oxidation of Ammonia Including the Formation and
at 0.25 MPa; Relevance of Combustion Enhancement to Flame Stability and Reduction of Nitrogen Oxides. Energy fuels. 32 (10), 10202–10217. doi:10.
NOx Control. Appl. Energy Combust. Sci. 7, 100038. doi:10.1016/j.jaecs.2021. 1021/acs.energyfuels.8b01056
100038 Shu, B., He, X., Ramos, C. F., Fernandes, R. X., and Costa, M. (2021). Experimental
Okafor, E. C., Naito, Y., Colson, S., Ichikawa, A., Kudo, T., Hayakawa, A., et al. and Modeling Study on the Auto-Ignition Properties of Ammonia/methane
(2018). Experimental and Numerical Study of the Laminar Burning Velocity of Mixtures at Elevated Pressures. Proc. Combust. Inst. 38 (1), 261–268. doi:10.
CH4-NH3-air Premixed Flames. Combust. flame 187, 185–198. doi:10.1016/j. 1016/j.proci.2020.06.291
combustflame.2017.09.002 Skalska, K., Miller, J. S., and Ledakowicz, S. (2010). Trends in NO Abatement: A
Otomo, J., Koshi, M., Mitsumori, T., Iwasaki, H., and Yamada, K. (2018). Chemical Review. Sci. total Environ. 408 (19), 3976–3989. doi:10.1016/j.scitotenv.2010.
Kinetic Modeling of Ammonia Oxidation with Improved Reaction Mechanism 06.001

Skreiberg, Ø., Kilpinen, P., and Glarborg, P. (2004). Ammonia Chemistry below Willmann, M., Berger, I., and Bärow, E. (2021). “Woodward L’Orange’s New
1400 K under Fuel-Rich Conditions in a Flow Reactor. Combust. Flame 136 (4), Injector Generation - an Ideal Platform for the Combustion of E-Fuels in Large
501–518. doi:10.1016/j.combustflame.2003.12.008 Engines,” in Heavy-Duty-, On- und Off-Highway-Motoren 2020. Editor J. Liebl
Smith, C., and Torrente-Murciano, L. (2021). Guidance for Targeted Development (Wiesbaden: Springer Vieweg Press), 223–240. doi:10.1007/978-3-658-
of Ammonia Synthesis Catalysts from a Holistic Process Approach. Chem. 34362-0_13
Catal. 1 (6), 1163–1172. doi:10.1016/j.checat.2021.09.015 Xiao, H., Lai, S., Valera-Medina, A., Li, J., Liu, J., and Fu, H. (2020). Experimental
Song, Y., Hashemi, H., Christensen, J. M., Zou, C., Marshall, P., and Glarborg, P. and Modeling Study on Ignition Delay of Ammonia/methane Fuels. Int.
(2016). Ammonia Oxidation at High Pressure and Intermediate Temperatures. J. Energy Res. 44 (8), 6939–6949. doi:10.1002/er.5460
Fuel 181, 358–365. doi:10.1016/j.fuel.2016.04.100 Yousefi, A., Guo, H., Dev, S., Liko, B., and Lafrance, S. (2022). Effects of Ammonia
Stagni, A., Cavallotti, C., Arunthanayothin, S., Song, Y., Herbinet, O., Battin- Energy Fraction and Diesel Injection Timing on Combustion and Emissions of
Leclerc, F., et al. (2020). An Experimental, Theoretical and Kinetic-Modeling an Ammonia/diesel Dual-Fuel Engine. Fuel 314, 122723. doi:10.1016/j.fuel.
Study of the Gas-phase Oxidation of Ammonia. React. Chem. Eng. 5 (4), 2021.122723
696–711. doi:10.1039/c9re00429g Yu, L., Zhou, W., Feng, Y., Wang, W., Zhu, J., Qian, Y., et al. (2020). The Effect of
Starkman, E. S., Newhall, H. K., Sutton, R., Maguire, T., and Farbar, L. (1967). Ammonia Ammonia Addition on the Low-Temperature Autoignition of N-Heptane: An
as a Spark Ignition Engine Fuel: Theory and Application. Sae Trans. 75, 765–784. Experimental and Modeling Study. Combust. Flame 217, 4–11. doi:10.1016/j.
Takizawa, K., Takahashi, A., Tokuhashi, K., Kondo, S., and Sekiya, A. (2008). combustflame.2020.03.019
Burning Velocity Measurements of Nitrogen-Containing Compounds. Yue, M., Lambert, H., Pahon, E., Roche, R., Jemei, S., and Hissel, D. (2021).
J. Hazard Mater 155 (1-2), 144–152. doi:10.1016/j.jhazmat.2007.11.089 Hydrogen Energy Systems: A Critical Review of Technologies, Applications,
Tay, K. L., Yang, W., Chou, S. K., Zhou, D., Li, J., Yu, W., et al. (2017). Effects of Trends and Challenges. Renew. Sustain. Energy Rev. 146, 111180. doi:10.1016/j.
Injection Timing and Pilot Fuel on the Combustion of a Kerosene-Diesel/ rser.2021.111180
ammonia Dual Fuel Engine: A Numerical Study. Energy Procedia 105, Zakaznov, V. F., Kursheva, L. A., and Fedina, Z. I. (1978). Determination of Normal
4621–4626. doi:10.1016/j.egypro.2017.03.1002 Flame Velocity and Critical Diameter of Flame Extinction in Ammonia-Air
The Royal Society (2020). Ammonia: Zero-Carbon Fertiliser, Fuel and Energy. https:// Mixture. Combust. Explos. Shock Waves 14 (6), 710–713. doi:10.1007/
royalsociety.org/-/media/policy/projects/green-ammonia/green-ammonia-policy- bf00786097
briefing.pdf (Accessed May 15, 2022). Zhang, Y., Davis, D., and Brear, M. J. (2022). The Role of Hydrogen in
Tian, Z., Li, Y., Zhang, L., Glarborg, P., and Qi, F. (2009). An Experimental and Decarbonizing a Coupled Energy System. J. Clean. Prod. 346, 131082.
Kinetic Modeling Study of Premixed NH3/CH4/O2/Ar Flames at Low Pressure. doi:10.1016/j.jclepro.2022.131082
Combust. Flame 156 (7), 1413–1426. doi:10.1016/j.combustflame.2009.03.005 Zhang, Y., Mathieu, O., Petersen, E. L., Bourque, G., and Curran, H. J. (2017).
Tock, L., Maréchal, F., and Perrenoud, M. (2015). Thermo-environomic Evaluation of the Assessing the Predictions of a NO X Kinetic Mechanism on Recent Hydrogen
Ammonia Production. Can. J. Chem. Eng. 93 (2), 356–362. doi:10.1002/cjce.22126 and Syngas Experimental Data. Combust. Flame 182, 122–141. doi:10.1016/j.
USGS (2021). Nitrogen Statistics and Information. https://www.usgs.gov/centers/ combustflame.2017.03.019
national-minerals-information-center/nitrogen-statistics-and-information (Accessed
May 15, 2022). Conflict of Interest: The authors declare that the research was conducted in the
Valera-Medina, A., Gutesa, M., Xiao, H., Pugh, D., Giles, A., Goktepe, B., Marsh, R., absence of any commercial or financial relationships that could be construed as a
and Bowen, P. (2019). Premixed Ammonia/hydrogen Swirl Combustion under potential conflict of interest.
Rich Fuel Conditions for Gas Turbines Operation. Int. J. Hydrogen Energy 44
(16), 8615–8626. doi:10.1016/j.ijhydene.2019.02.041 Publisher’s Note: All claims expressed in this article are solely those of the authors
Valera-Medina, A., Xiao, H., Owen-Jones, M., David, W. I. F., and Bowen, P. J. and do not necessarily represent those of their affiliated organizations, or those of
(2018). Ammonia for Power. Prog. Energy Combust. Sci. 69, 63–102. doi:10. the publisher, the editors, and the reviewers. Any product that may be evaluated in
1016/j.pecs.2018.07.001 this article, or claim that may be made by its manufacturer, is not guaranteed or
Wang, S., Wang, Z., Elbaz, A. M., Han, X., He, Y., Costa, M., Konnov, A. A., and endorsed by the publisher.
Roberts, W. L. (2020). Experimental Study and Kinetic Analysis of the Laminar
Burning Velocity of NH3/syngas/air, NH3/CO/air and NH3/H2/air Premixed Copyright © 2022 Tornatore, Marchitto, Sabia and De Joannon. This is an open-
Flames at Elevated Pressures. Combust. Flame 221, 270–287. doi:10.1016/j. access article distributed under the terms of the Creative Commons Attribution
combustflame.2020.08.004 License (CC BY). The use, distribution or reproduction in other forums is permitted,
Wang, Z., Han, X., He, Y., Zhu, R., Zhu, Y., Zhou, Z., et al. (2021). Experimental provided the original author(s) and the copyright owner(s) are credited and that the
and Kinetic Study on the Laminar Burning Velocities of NH3 Mixing with original publication in this journal is cited, in accordance with accepted academic
CH3OH and C2H5OH in Premixed Flames. Combust. Flame 229, 111392. practice. No use, distribution or reproduction is permitted which does not comply
doi:10.1016/j.combustflame.2021.02.038 with these terms.

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published: 22 July 2022

Ammonia as Green Fuel in Internal

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FIGURE 2 | Green ammonia production through electrolysis of water + Haber–Bosch process.

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TABLE 1 | Combustion properties of NH3 and other hydrocarbon fuels.

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FIGURE 4 | SL as a function of the fuel “enhancer” addition (reported as %) or of the O2 content.

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recently updated the rate constants of H2NO + O2 = HNO +

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Titania and Other Metal Oxides. J. Photochem. Photobiol. A Chem. 88 (1),

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