energies

Review
Ammonia as Effective Hydrogen Storage: A Review
on Production, Storage and Utilization
Muhammad Aziz 1, * , Agung Tri Wijayanta 2 and Asep Bayu Dani Nandiyanto 3
1 Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan
2 Mechanical Engineering Department, Engineering Faculty, Sebelas Maret University,
Surakarta 57126, Indonesia; [email protected]
3 Departemen Kimia, Universitas Pendidikan Indonesia, Bandung 40154, Indonesia; [email protected]
* Correspondence: [email protected]; Tel.: +81-3-5452-6196




Received: 18 March 2020; Accepted: 10 June 2020; Published: 12 June 2020


Abstract: Ammonia is considered to be a potential medium for hydrogen storage, facilitating

CO2 -free energy systems in the future. Its high volumetric hydrogen density, low storage pressure
and stability for long-term storage are among the beneficial characteristics of ammonia for hydrogen
storage. Furthermore, ammonia is also considered safe due to its high auto ignition temperature,
low condensation pressure and lower gas density than air. Ammonia can be produced from many
different types of primary energy sources, including renewables, fossil fuels and surplus energy
(especially surplus electricity from the grid). In the utilization site, the energy from ammonia can
be harvested directly as fuel or initially decomposed to hydrogen for many options of hydrogen
utilization. This review describes several potential technologies, in current conditions and in the
future, for ammonia production, storage and utilization. Ammonia production includes the currently
adopted Haber–Bosch, electrochemical and thermochemical cycle processes. Furthermore, in this
study, the utilization of ammonia is focused mainly on the possible direct utilization of ammonia
due to its higher total energy efficiency, covering the internal combustion engine, combustion for gas
turbines and the direct ammonia fuel cell. Ammonia decomposition is also described, in order to
give a glance at its progress and problems. Finally, challenges and recommendations are also given
toward the further development of the utilization of ammonia for hydrogen storage.

Keywords: ammonia; hydrogen; production; storage; utilization; CO2 free

1. Introduction
The adoption of fossil fuels in conventional energy systems has led to the increase of the
concentration of greenhouse gases (GHGs) in the atmosphere and the rise of ocean levels [1]. Being aware
of this reality, recently, the adoption of renewable energy has increased rapidly due to its low
environmental impacts. In addition, the massive deployment and the maturity of technology have
made renewable energy economic and competitive against conventional fossil fuels. It is expected that a
clean and CO2 -free energy system can be realized to improve the quality of human life. The Conference
of Parties 21 (COP21), held in 2015, issued the world commitments to the mitigation of climate change
and keeping the increase of the global average temperature below 2 ◦ C higher than the pre-industrial
level [2]. Moreover, the Marrakech Partnership for Global Climate Action has strongly promoted
collective striving for the 1.5 ◦ C temperature goal through mutual collaboration among governments,
regions, businesses and investors [3].
Liberalization and decentralization in the energy sector has also opened up the opportunity to
the customers to behave simultaneously as energy producer and consumer. The fluctuating demand
and supply sides in the future energy system also require an effective adoption of secondary energy

Energies 2020, 13, 3062; doi:10.3390/en13123062 www.mdpi.com/journal/energies

Energies 2020, 13, 3062 2 of 25

sources (energy carriers) which can be effectively and economically produced, stored and utilized.
The future energy system is expected to be able to facilitate the optimum utilization of local energy
resources (especially renewable energy) [4], reduction of global GHG emission, improvement of
urban environmental quality and creation of industrial activities focusing the energy sector toward a
sustainable economy [5].
Hydrogen (H2 ) is one of the secondary energy sources which produces no GHG by-products
during its utilization, because the oxidation of hydrogen generates water (H2 O). It is the most abundant
element in the universe (more than 90% of the total available atoms), the lightest element (molecular
weight of 2.016) and non-toxic [6]. Hydrogen has significantly higher gravimetric energy density
(120 MJ/kg) compared to other conventional fuels, such as gasoline (44 MJ/kg). In addition, hydrogen can
be produced from various kinds of primary energy sources, including renewables and non-renewables.
Many technological routes are available, including thermochemical routes (gasification, chemical
looping, reforming), biochemical routes (fermentation) and electrolysis [7]. Furthermore, the utilization
of hydrogen as an energy source can also be performed via various technologies, such as fuel cells,
combustion and mixing with other fuels. However, hydrogen suffers a disadvantage in its volumetric
energy density, which is only 3 Wh/L, leading to difficulties in its storage. Hydrogen storage is the
key enabling technology which will lead to the successful deployment of hydrogen, including its
economic sustainability.
There are several key parameters in the selection of hydrogen storage methods and materials,
including: (a) gravimetric and volumetric hydrogen densities, (b) energy efficiency, (c) refueling time,
(d) durability, (e) cost, (f) standards, (g) technology maturity and (h) life-cycle and efficiency analysis [8].
Energy efficiency deals with the energy consumed during both the storage and release of hydrogen to
and from its storage states or hydrogen storage materials. Furthermore, durability is correlated to its
lifetime, especially in case of reversible hydrogen storage materials. Standards for the storage systems
and interface are required in order to facilitate the implementation of the storage technology, as well as
safety and public acceptance. The successful development of hydrogen storage is crucial for the future
of hydrogen economy [9,10].
In order to store hydrogen effectively, different hydrogen storage technologies have been studied
and developed. These include compressed and liquefied hydrogen, liquid organic carriers [11], metal
hydrides [12,13], methanol (CH3 OH) and ammonia (NH3 ). Hydrogen storage covers both mobile
and stationary systems. Compressed hydrogen is the simplest way to store hydrogen, although its
hydrogen density is low (42.2 kg-H2 /m3 at 69 MPa). Compressed hydrogen requires high pressure
to effectively store the gaseous hydrogen. In the case of a hydrogen vehicle, a high pressure tank of
about 70 MPa is currently required in order to store the hydrogen to achieve a similar driving range
to conventional vehicles. Moreover, as hydrogen is a very light and small element, leakage from
high pressure can easily occur, in addition to the problem related to hydrogen embrittlement. Liquid
hydrogen is also considered promising and efficient as a hydrogen storage option, because it has
higher hydrogen density (70.8 kg-H2 /m3 ), which is about 800 times that of uncompressed hydrogen
(0.08988 kg/m3 at standard temperature and pressure (STP)), as well as high purity. However, in order
to bring hydrogen into the liquid phase, refrigeration to a very low temperature (−253 ◦ C) is required,
leading to high energy consumption. Moreover, due to this cooling requirement, liquid hydrogen is not
preferred for long term storage or long distance of transportation, because the energy input needed to
keep the temperature very low is also intensive. Another problem of liquid hydrogen is the conversion
of ortho-hydrogen (where the spins of both nuclei are in the same direction) to para-hydrogen (where
the spins of both nuclei are in opposite directions) [14]. As this isomer conversion is exothermic, the
generated heat causes the boil-off phenomenon, in which a part of liquid hydrogen is evaporated into
a gaseous form.
Solid-state systems are also considered a potential hydrogen storage method. They can reversibly
adsorb and release hydrogen. The storage of hydrogen occurs by two different methods: physisorption
and chemisorption [15,16]. In the former, hydrogen molecules are adsorbed on the surface of
Energies 2020, 13, 3062 3 of 25

an adsorbent (storage medium) due to the intermolecular force that exists between the adsorbate
(hydrogen) and adsorbent. Physisorption hydrogen storages include carbon nanotubes, activated
carbon, zeolites and metal-organic frameworks (MOFs). These materials are advantageous in terms of
their reversibility and relatively fast kinetics. However, they have several disadvantages, including low
hydrogen storage (lower than 5 wt% at room temperature) and their requirement of low temperatures
for larger hydrogen storage capacities [17,18]. On the other hand, in chemisorption hydrogen storage,
hydrogen chemically reacts with solids, producing hydrides. These hydrides can be categorized into
metal, complex and chemical hydrides. Recently, various complex hydrides have been developed,
including NaAlH4 , Mg(NH2 )2 -LiH. Although these materials show high hydrogen density (up to
10 wt%), their hydrogenation and dehydrogenation are very complex and their reversibility is relatively
low [19,20]. In addition, these processes also lead to the decrease of energy efficiency, especially the
dehydrogenation process, which is generally endothermic.
Methanol is also a promising candidate for hydrogen storage, as well the utilization of CO2 via
hydrogenation [21]. The adoption of methanol is strongly correlated with the idea of power-to-product
(P2X), which utilizes surplus electricity to produce chemical fuels. Hydrogen can be released from
methanol through thermolysis, steam reforming and partial oxidation [21]. However, the adoption
of methanol to store hydrogen leads to environmental problems in the utilization site because of the
release of CO2 when methanol is directly utilized or decomposed. This leads to a non CO2 -free energy
system. In addition, the separation of CO2 is also energy intensive. The established CO2 separation
based on absorption using amine solution consumes approximately 1.1 kWh/kg-CO2 [22].
On the other hand, ammonia is highly valued as a potential hydrogen storage option. It has
high hydrogen density (17.8 wt%), as well as high flexibility in its utilization, including mobile and
stationary applications. Due to its stability for long-term storage and transportation, ammonia can
fulfill the demand to store the energy in time (stationary energy storage) and in space (energy export
and import) [23]. Ammonia can be utilized by extracting its stored hydrogen or directly utilized as fuel.
Ammonia is currently adopted as an agricultural fertilizer, refrigerant gas and in the manufacture of
explosives, pesticides and other chemicals. Therefore, the infrastructures to produce, store, transport
and utilize ammonia have been globally established [24], leading to its proven economic performance.
In addition, regulations and procedure for ammonia handling have been established well in the world.
The ammonia economy has been investigated in numerous studies, including studies of islanded
systems [25], process modeling and fertilizer production using renewable energy [23]. However, for
applications in the energy sector, ammonia still faces various challenges, including its properties,
conversion technologies and possible environmental problems following its utilization.
Figure 1 shows the possible routes for the production and utilization of ammonia. Ammonia
can be produced from both fossil fuels and renewable energy sources. These primary energy sources
are then converted to ammonia through several processes, including pre-treatment, conversion and
synthesis. In addition, the surplus electricity can also be converted to hydrogen [26], which is further
converted to ammonia, leading to the application of power-to-ammonia. The produced ammonia is
then stored, transported and distributed to the users for its utilization. Numerous countries in the
world have a strong motivation to utilize ammonia as one of key players in future energy system.
Therefore, these countries have tried to set the future road map, as well as developing the technologies
to realize the plan. Japan has clearly decided its plan for ammonia adoption. The ammonia supply
chain in the energy sector has been targeted for realization by 2030 [27]. In the beginning, 300 kW-class
gas turbines will be tested until the end of 2020. Moreover, other movements to utilize ammonia,
including advanced combined cycles, direct ammonia-fueled fuel cells and the co-firing of ammonia at
existing coal-fired power plants, have also been started [28]. Australia has also accelerated research
and development programs for ammonia utilization in order to store the produced hydrogen by the
country and then export it to other countries [29]. Similar research motivation to push the adoption of
ammonia has also been shown by the UK [30] and Germany [31]. In addition, the electricity generation
and industrial sectors have been targeted as the first projected market.
Energies 2020, 13, 3062 4 of 25
Energies 2020, 13, x FOR PEER REVIEW 4 of 25

Figure 1. Production and utilization routes of ammonia in

in the
the energy
energy sector.
sector.

This
This work
work reviews
reviews potential
potential technologies,
technologies, covering
covering the
the production,
production, storage
storage and
and utilization
utilization of
of
ammonia, as well as its important role in the energy system. Section 2 describes the characteristics
ammonia, as well as its important role in the energy system. Section 2 describes the characteristics of of
ammonia,
ammonia, especially
especially in
in terms
terms of
of its
its advantages
advantages and disadvantages as
and disadvantages as aa hydrogen
hydrogen storage
storage mechanism.
mechanism.
Section
Section 33 explains
explains several
several possible
possible ammonia
ammonia production
production technologies,
technologies, including
including conventional
conventional andand
advanced production systems. Section 4 describes potential ammonia storage
advanced production systems. Section 4 describes potential ammonia storage methods, especially methods, especially
liquid
liquid ammonia.
ammonia. Furthermore,
Furthermore, the the utilization
utilization of
of ammonia
ammonia is is described
described in in Section
Section 5,
5, especially
especially direct
direct
utilization
utilizationtechnologies.
technologies.The Thedecomposition
decompositionofofammonia
ammonia and
andseparation
separation of the hydrogen
of the hydrogen gas gas
stream are
stream
also described in this section. Challenges and recommendations related to the
are also described in this section. Challenges and recommendations related to the adoption of adoption of ammonia
are discussed
ammonia are in Section 6.
discussed in Finally,
Section Section 7 concludes
6. Finally, Section 7 the points reviewed
concludes the pointsin this work.
reviewed in this work.

2. Characteristics of Ammonia
2. Characteristics of Ammonia
2.1. Physical Properties
2.1. Physical Properties
Ammonia is alkaline, colorless and has a relatively strong odor. Table 1 shows the detailed
Ammonia is alkaline, colorless and has a relatively strong odor. Table 1 shows the detailed
parameters of the physical properties of ammonia. From techno-economic analysis, ammonia is
parameters of the physical properties of ammonia. From techno‐economic analysis, ammonia is
considered to be the least expensive fuel compared to other conventional fuels, such as gasoline,
considered to be the least expensive fuel compared to other conventional fuels, such as gasoline,
natural gas, liquefied petroleum gas (LPG), methanol and hydrogen [32]. In addition, liquid ammonia
natural gas, liquefied petroleum gas (LPG), methanol and hydrogen [32]. In addition, liquid ammonia
has a relatively high volumetric energy density, 12.7 MJ/L, which is higher than liquid hydrogen
has a relatively high volumetric energy density, 12.7 MJ/L, which is higher than liquid hydrogen (8.49
(8.49 MJ/L) and compressed hydrogen (4.5 MJ/L at pressure of 69 MPa and temperature of 25 ◦ C).
MJ/L) and compressed hydrogen (4.5 MJ/L at pressure of 69 MPa and temperature of 25 °C). The
The boiling temperature of ammonia is −33.4 ◦ C at atmospheric pressure. Furthermore, ammonia has
boiling temperature of ammonia is −33.4 °C at atmospheric pressure. Furthermore, ammonia has a
a significantly higher combustion heat, 11.2 MJ/L, compared to liquid hydrogen (8.58 MJ/L).
significantly higher combustion heat, 11.2 MJ/L, compared to liquid hydrogen (8.58 MJ/L).
Gaseous ammonia can dissipate very quickly in the air under atmospheric conditions due to its
Gaseous ammonia can dissipate very quickly in the air under atmospheric conditions due to its
lighter density than the air (0.769 kg/m33 compared to 1.225 kg/m33 at STP), minimizing explosion and
lighter density than the air (0.769 kg/m compared to 1.225 kg/m at STP), minimizing explosion and
fire risks in case of leakage. Furthermore, as ammonia has a higher auto ignition temperature (650 ◦ C)
fire risks in case of leakage. Furthermore, as ammonia has a higher auto ignition temperature (650
than hydrogen (520 ◦ C), ammonia has a lower risk of fire than hydrogen. The apparent toxicity (vapor
°C) than hydrogen (520 °C), ammonia has a lower risk of fire than hydrogen. The apparent toxicity
pressure relative to toxicity at atmospheric temperature) of liquid ammonia is about three orders of
(vapor pressure relative to toxicity at atmospheric temperature) of liquid ammonia is about three
magnitude higher than gasoline and methanol. This is due to the phenomenon that liquid ammonia
orders of magnitude higher than gasoline and methanol. This is due to the phenomenon that liquid
has an immediately dangerous to life or health (IDLH) concentration of about 300 ppm, but its vapor
ammonia has an immediately dangerous to life or health (IDLH) concentration of about 300 ppm, but
pressure is relatively high; 8.58 × 102 kPa at 202 ◦ C [33].
its vapor pressure is relatively high; 8.58 × 10 kPa at 20 °C [33].
The challenges faced by ammonia include its narrow flammability range, which is 15.15–27.35%
in dry air and 15.95–26.55% in 100% relative humidity air. Hence, it is usually considered to be
Table 1. Detailed physical characteristics of ammonia [34,35].
non-flammable during its storage and transportation. In addition, as ammonia has nitrogen as its
main component, the utilization ofProperties
ammonia, especially in high temperatures,Unit potentially
Valueleads to NOx
Molar mass g/mol 17.031
formation. Therefore, the combustion management of ammonia is crucial. Moreover, as ammonia is
categorized as a toxic chemical, itDensity at STPto carry out appropriate hazard
is important kg/m3management
0.769 in order to
mitigate its danger to humanity Melting point
and the environment. °C −77.73
Boiling point at 100 kPa °C −33.4
Vapor pressure at 20 °C kPa 858
Heat of evaporation MJ/kg 1.371
Energies 2020, 13, 3062 5 of 25

Table 1. Detailed physical characteristics of ammonia [34,35].

Properties Unit Value

Molar mass g/mol 17.031
Density at STP kg/m3 0.769
Melting point ◦C −77.73
Boiling point at 100 kPa ◦C −33.4
Vapor pressure at 20 ◦ C kPa 858
Heat of evaporation MJ/kg 1.371
Auto ignition temperature ◦C 650
Critical temperature ◦C 132.4
Critical pressure MPa 11.28
Viscosity at 25 ◦ C µPa·s 10.07
Heat capacity at constant pressure (101.325 kPa, 15 ◦ C) kJ/mol·◦ C 0.037
Heat capacity at constant volume (101.325 kPa, 15 ◦ C) kJ/mol·◦ C 0.028
Heat of combustion MJ/L 11.2
Thermal conductivity mW/m·◦ C 22.19
Critical density g/mL 0.24
Condensation pressure at 25 ◦ C MPa 0.99
Flammability limit (equivalence ratio) - 0.63–1.4
Adiabatic flame temperature ◦C 1800
Max. laminar burning velocity m/s 0.07

2.2. Hydrogen Storage Performance

Table 2 lists the characteristics comparison of hydrogen storage methods, including compressed
hydrogen, liquid hydrogen, methanol and liquid ammonia. Liquid ammonia is able to store hydrogen
in volumes much higher (121 kg-H2 /m3 ) than liquid hydrogen (70.8 kg-H2 /m3 ), which is about 1.7 times
as high. Liquid ammonia can be stored at relatively low pressure (0.99 MPa at a temperature of 25 ◦ C),
which is significantly lower than that of compressed hydrogen. However, in terms of physical density,
liquid ammonia has the higher density (600 kg/m3 ) than compressed and liquid hydrogen, leading to
heavier storage and transportation.
Methanol is a strong competitor for the storage of hydrogen. It has higher energy density than
ammonia (20.1 MJ/kg compared to 18.6 MJ/kg). However, it has both lower gravimetric and volumetric
hydrogen contents than ammonia (12.5 wt% and 99 kg-H2 /m3 compared to 17.8 wt% and 121 kg-H2 /m3 ,
respectively) [36]. As methanol involves CO2 in its synthesis, its utilization and decomposition also
release CO2 , leading to the environmental concerns. Methanol reformation also leaves the problem of
the production of carbon monoxide (CO), which can poison most of the catalysts adopted in fuel cells,
and hence shortens the life time of the fuel cell [37].

Table 2. Characteristics comparison of compressed hydrogen, liquid hydrogen, methanol and liquid
ammonia [36,38,39].

Compressed Liquid Liquid

Properties Unit Methanol
Hydrogen Hydrogen Ammonia
Storage method - Compression Liquefaction Ambient Liquefaction
Temperature ◦C 25 (room) −252.9 25 (room) 25 (room)
Storage pressure MPa 69 0.1 0.1 0.99
Density kg/m3 39 70.8 792 600
Explosive limit in air %vol 4–75 4–75 6.7–36 15–28
Gravimetric energy density
MJ/kg 120 120 20.1 18.6
(LHV)
Energies 2020, 13, 3062 6 of 25

Table 2. Cont.

Compressed Liquid Liquid

Properties Unit Methanol
Hydrogen Hydrogen Ammonia
Volumetric energy density
MJ/L 4.5 8.49 15.8 12.7
(LHV)
Gravimetric hydrogen content wt% 100 100 12.5 17.8
Volumetric hydrogen content kg-H2 /m3 42.2 70.8 99 121
Catalytic Catalytic
Hydrogen release - Pressure release Evaporation decomposition decomposition
T > 200 ◦ C T > 400 ◦ C
Energy to extract hydrogen kJ/mol-H2 - 0.907 16.3 30.6

To release the hydrogen from ammonia, a relatively huge amount of energy is consumed
(30.6 kJ/mol-H2 ). On the other hand, the regasification of liquid hydrogen only consumes very low
energy (0.907 kJ/mol-H2 ). Therefore, ammonia decomposition is a challenging task, especially in
terms of total energy efficiency in the utilization of ammonia. The decomposition of ammonia must
be followed by hydrogen separation in the case that a high purity of hydrogen is demanded at the
utilization site. On the other hand, compressed and liquid hydrogen can deliver highly pure hydrogen.

3. Ammonia Production
Currently, about 200 Mt/y of ammonia is manufactured globally [40], making it the world’s second
most commonly produced chemical after sulfuric acid (H2 SO4 ). Similarly to hydrogen, ammonia can
be produced from different primary energy sources, including biomass, coal, natural gas, solar, wind,
geothermal, hydro and nuclear sources. Ammonia can be produced through different conversion
technologies: thermochemical, electrochemical, photochemical and plasma [41]. However, with the
consideration of technological feasibility and total energy efficiency [42,43], in this work, three main
conversion technologies (Haber–Bosch, electrochemical and thermochemical cycle processes) are
described. Furthermore, recent trends in the development of enhanced systems in order to improve
the total energy efficiency during ammonia production are also described.

3.1. Conventional Ammonia Production (Haber–Bosch Process)

The currently adopted ammonia production process basically employs the system invented
by Fritz Haber and Carl Bosch about 100 years ago [40]. Therefore, this system is well known as
Haber–Bosch process. About 85% of total production of ammonia worldwide is produced by this
process [44]. The ammonia synthesis occurs according to reaction (1).

3 H 2 + N2 2 NH3 ∆H◦ 27 ◦ C = −46.35 kJ/mol (1)

Ammonia synthesis is an exothermic reaction (negative enthalpy change), and it occurs

spontaneously at low temperatures (negative entropy change). Although it is favored at room
temperature, the reaction rate at which the reaction occurs at room temperature is too slow to be
applicable for at an industrial scale. In order to increase the kinetics of the reaction to achieve the
targeted conversion rate, high pressure and temperature are required. To effectively synthesize
ammonia from its main components (hydrogen and nitrogen), the reaction should be performed at a
relatively high temperature and pressure of 400–500 ◦ C and 10–30 MPa, respectively, with the assistance
of an iron-based catalyst. This condition is demanded due to the high dissociation energy (941 kJ/mol)
of triple-bonded nitrogen. However, to bring the reaction under this high temperature and pressure,
about 30 MJ/kg-NH3 of energy is required [45].
The production of ammonia from natural gas is conducted by reacting methane (natural gas) with
steam and air, coupled with the subsequent removal of water and CO2 . The products of this process
are hydrogen and nitrogen, which are the feedstock for the main ammonia synthesis. During the
Energies 2020, 13, 3062 7 of 25

Energies 2020, 13, x FOR PEER REVIEW 7 of 25

process, the removal of sulfur and other impurities is important, because they can reduce and damage
the performance
where the catalyst of the catalyst during
is immersed inside. synthesis. In the ammonia
The produced ammonia, synthesis
together process,
with the bothunreacted
nitrogen
and hydrogen
hydrogen, areand
argon compressed to relatively
other impurities, highcooled
is then pressure downto beforfedammonia
to the synthesis reactor,inwhere
condensation orderthe
to
catalyst is immersed inside. The produced ammonia, together with the
separate the ammonia from the other gases. The unreacted hydrogen and nitrogen are then recycled unreacted hydrogen, argon and
other impurities,
back and is then cooled
mixed together with the down
newfor ammonia
feedstock. Tocondensation
avoid a build‐up in order to separate
of impurities, suchtheasammonia
argon, a
from the other gases. The unreacted hydrogen and nitrogen are then
small part of the gases is purged from the process. Ammonia synthesis produces a small amount of recycled back and mixed together
with
heat, the
whichnewisfeedstock.
released from To avoid a build-up
the reactor; of impurities,
therefore, such as argon,
it can be recovered a small for
and utilized part of the
other gases is
processes,
purged
such asfromsteam theand
process.
power Ammonia
generation. synthesis produces
In general, abouta small
88%amount of heat, which
of hydrogen’s calorificis released
value can from
be
the reactor;
conserved [46]. therefore, it can be recovered and utilized for other processes, such as steam and power
generation.
Another Inchallenge
general, about in the88% of hydrogen’s
Haber–Bosch calorific
process is itsvalue can be conserved
low conversion [46].
rate; therefore, the process
mustAnother
be recycledchallenge
to achieve in the Haber–Bosch
the process isflow
expected production its lowrate.conversion
However,rate; therefore,
at pressure theMPa,
of 30 process
the
must be recycled to achieve the expected production flow rate. However,
conversion rate from the reaction is still low, no more than 25% [47]. This stream recirculation causes at pressure of 30 MPa, the
conversion
some problems, rate from
includingthe reaction
the need isfor
stillanlow, no morerecirculation
additional than 25% [47]. Thisand
system stream recirculation
a larger causes
reactor, leading
some
to highproblems,
investment including the needcosts.
and operation for an additional recirculation system and a larger reactor, leading
to high investment and operation costs.
When hydrogen is produced via water electrolysis, nitrogen can be supplied via air separation.
When hydrogen
Air separations is produced
for nitrogen via water
production can electrolysis,
be conducted nitrogen can be supplied
via membrane, cryogenic, viaabsorption
air separation.
and
Air separations for nitrogen production can be conducted via membrane,
adsorption technologies [48]. For large scales, cryogenic separation is considered more economical cryogenic, absorption and
adsorption technologies
than other methods. [48]. For cryogenic
In addition, large scales, aircryogenic
separationseparation
could produceis considered more of
a high purity economical
products
than
[49]. other methods. In addition, cryogenic air separation could produce a high purity of products [49].
The
The energy consumed during
energy consumed during ammonia
ammonia production,
production, including
including conversion
conversion from from primary
primary sources,
sources,
typically
typically ranges
ranges from
from aboutabout 28 28 to
to 37
37 GJ/t
GJ/t [44].
[44]. An
An ammonia
ammonia production
production system
system from from anyany primary
primary
source,
source, such as natural gas, is considered complex, as it includes many combined processes. Figure 22
such as natural gas, is considered complex, as it includes many combined processes. Figure
shows
shows thethe schematic
schematic diagram
diagram of of conventional
conventional ammoniaammonia production
production from from natural
natural gas.
gas. The
The system
system
consists
consists ofof different
different processes:
processes: steamsteam reformation,
reformation, the the water–gas
water–gas shift shift reaction,
reaction, CO CO22 removal,
removal, syngas
syngas
purification, and ammonia synthesis and separation. Therefore, efforts
purification, and ammonia synthesis and separation. Therefore, efforts to reduce the total energy to reduce the total energy
consumption
consumption require
requirethe theimprovement
improvementofofthe thewhole
wholeprocess
process involved.
involved. Due Duetotohigh
highenergy
energy intensity of
intensity
ammonia
of ammonia production,
production, ammonia
ammonia synthesis emitsemits
synthesis a totala of 289.8
total of Mt-CO 2 annually
289.8 Mt‐CO [25], which
2 annually [25], is almost
which is
0.93% of global CO
almost 0.93% of global 2 emissions [50].
CO2 emissions [50].

Schematic
Figure 2.2.Schematic diagram
diagram of ammonia
of ammonia production
production fromgas,
from natural natural gas, the
employing employing the
Haber–Bosch
Haber–Bosch
process. process.

Focusing
Focusing on on the
the Haber–Bosch
Haber–Bosch process,
process, many
many efforts
efforts to
to reduce
reduce its
its extreme
extreme conditions
conditions have
have been
been
carried
carried out. They include the introduction of an extra component in order to inhibit the catalysis and
out. They include the introduction of an extra component in order to inhibit the catalysis and
the
the alteration of geometry and electronic nature of the reacting components in order to optimize the
alteration of geometry and electronic nature of the reacting components in order to optimize the
energetics
energetics of
of catalysis
catalysis [51]. Ru-based catalysts
[51]. Ru‐based catalysts can
can basically
basically facilitate
facilitate ammonia
ammonia synthesis
synthesis under
under mild
mild
conditions ◦ and pressure of 4–15 MPa), which is significantly lower than
conditions (at
(ataatemperature
temperatureofof300–450
300–450C°C and pressure of 4–15 MPa), which is significantly lower
the conditions required for iron-based catalysts.
than the conditions required for iron‐based catalysts. However, Ru-based
However, catalysts
Ru‐based are expensive
catalysts and suffer
are expensive and
from
sufferhydrogen poisoning
from hydrogen [52,53]. Alkaline
poisoning earth metal
[52,53]. Alkaline oxides
earth andoxides
metal hydroxides have been identified
and hydroxides have beenas
identified as promoters to improve the catalytic performance of Ru‐based catalysts [54]. Several
electrides (crystals in which electrons serve as anions), such as Ca2N:e−, which can be deposited in Ru
nanoparticles have the potential to facilitate ammonia synthesis at 200 °C [55]. Transition metals (TM)
Energies 2020, 13, 3062 8 of 25

Energies 2020, 13, x FOR PEER REVIEW 8 of 25

promoters to improve the catalytic performance of Ru-based catalysts [54]. Several electrides (crystals
in
canwhich electrons synthesis
also improve serve as anions),
performance, Ca2 N:e− , which
such asincluding canthe
lowering be deposited in Ru
pressure and nanoparticles
temperature. have
This is
the ◦
duepotential to facilitate
to the existence ofammonia synthesis between
scaling relations at 200 C the[55].transition‐state
Transition metals (TM) required
energy can also improve
for the
synthesis
dissociation performance,
of nitrogenincluding
and the lowering
adsorptiontheenergy
pressureofand temperature.
all the This is
intermediates due toFurthermore,
[56,57]. the existence
of scaling relations between the transition-state energy required for the dissociation
Kawamura and Taniguchi [58] have tested sodium melt as a catalyst for ammonia synthesis. By of nitrogen and the
using
adsorption
this type ofenergy
catalyst, of the
all the intermediates
synthesis could be[56,57].
carriedFurthermore, Kawamura
out at reaction and Taniguchi
temperatures of 500–590 [58]
°Chave
and
tested sodium melt as a catalyst for ammonia synthesis. By using this type
atmospheric pressure. However, further analysis and experimentation are required to bring this of catalyst, the synthesis
could
method betocarried
the leveloutofatbeing
reaction temperatures of 500–590 ◦ C and atmospheric pressure. However,
applicable.
further analysis and experimentation are required to bring this method to the level of being applicable.
3.2. Electrochemical Processing
3.2. Electrochemical Processing
Although electrochemical processing is significantly under‐developed compared to the Haber–
Bosch process, itelectrochemical
Although processing
is expected to realize higher is energy
significantly under-developed
performance. The energy compared
consumed by to this
the
Haber–Bosch process, it is expected to realize higher energy performance. The
process is about 20% lower than the Haber–Bosch process [59]. Figure 3 shows the schematic flow energy consumed by
this process is about 20% lower than the Haber–Bosch process [59]. Figure
diagram of electrochemical ammonia synthesis. The process is considered simple; therefore, its 3 shows the schematic
flow diagram
application is of electrochemical
considered ammonia
to potentially synthesis.
reduce system The process is considered
configuration and control simple; therefore,
complexity. In
its application is considered to potentially reduce system configuration
addition, the investment cost can be lower compared to currently adopted ammonia synthesis and control complexity. In
addition,
systems. the investment cost can be lower compared to currently adopted ammonia synthesis systems.

Figure 3. Schematic diagram of electrochemical ammonia synthesis.

The
The reactions
reactionsatatboth
bothcathode
cathodeand
andanode inin
anode proton conducting
proton conductingcells are are
cells shown in reactions
shown (2) and
in reactions (2)
(3), respectively. The reactions at each cathode and anode are basically reversible.
and (3), respectively. The reactions at each cathode and anode are basically reversible.
N2 +N62 H + 6 +e−+⇌6 2e−NH32 NH3
+ 6+H (2)
(2)

3 H23⇌ + 6 +e−+ 6 e−
H62 H 6+ H (3)
(3)
Four different
Four different types
typesofofelectrolytes
electrolytesare
arecurrently
currently available:
available:(a) (a)
liquid electrolytes,
liquid (b) molten
electrolytes, salt,
(b) molten
(c) composite membranes and (d) solid state electrolytes. Liquid electrolytes can
salt, (c) composite membranes and (d) solid state electrolytes. Liquid electrolytes can operate under operate under
atmospheric temperature
atmospheric temperature and and pressure [60]. There
pressure [60]. There are some potential
are some potential liquid
liquid electrolytes,
electrolytes, including
including
LiClO 4 (0.2 M) in tetrahydrofuran [60], LiClO4 in ionic liquid, LiClO4 in H2SO4 and Li2SO4 in H2SO4
LiClO4 (0.2 M) in tetrahydrofuran [60], LiClO4 in ionic liquid, LiClO4 in H2 SO4 and Li2 SO4 in
[61]. Ammonia production of 3.68 × 10−10 mol/cm2−10 ∙s could be obtained,
2 ·s could be while the system efficiency can
H 2 SO4 [61]. Ammonia production of 3.68 × 10 mol/cm obtained, while the system
reach about
efficiency 58%,
can indicating
reach about 58%,thatindicating
about 58%thatof the
aboutcurrent
58% supplied to thesupplied
of the current system istoconverted
the system into
is
ammonia. However, the research related to this issue is still limited to lab experiments,
converted into ammonia. However, the research related to this issue is still limited to lab experiments, in small
dimensions
in of cells and
small dimensions limited
of cells andoperation times [41].
limited operation times [41].
A molten salt type electrolyte is generally operated at a temperature range of 300–500 °C [62].
There are some potential chemicals for use as electrolytes, such as LiCl, KCl and CsCl, with dissolved
Li3N [63]. The reported ammonia production rate is 3.3 × 10−9 mol/cm2∙s, and the efficiency is about
72%. Moreover, the system with composite electrolytes also includes solid electrolytes, which are
Energies 2020, 13, x FOR PEER REVIEW 9 of 25

combined with low melting salt, and have an operating temperature of 300–700 °C. The electrolytes
Energies
comprise 13, main
2020,the 3062 ionic conducting phase and an additional phase that is attached to the main phase
9 of 25
to improve the electrical, mechanical and thermal properties [33]. As the representative of composite
electrolytes, alkali metal carbonate (such as LiCO3) and oxide (such as LiAlO2) and CeO2 doped with
A molten salt type electrolyte is generally operated at a temperature range of 300–500 ◦ C [62].
Sm2O3 have shown the expected properties, including oxygen ion, carbonate ion and proton
There are some potential chemicals for use as electrolytes, such as LiCl, KCl and CsCl, with dissolved
conductivity [64]. In addition, Amar et al. [64] have tested mixed Na, K and Li carbonates, in addition
Li3 N [63]. The reported ammonia production rate is 3.3 × 10−9 mol/cm2 ·s, and the efficiency is about
to the LiAlO2, as the electrolyte. They obtained an ammonia production rate of 2.32 × 10−10 mol/cm2∙s
72%. Moreover, the system with composite electrolytes also includes solid electrolytes, which are
at a temperature of about 400 °C. The system with solid electrolytes generally operates in very wide
combined with low melting salt, and have an operating temperature of 300–700 ◦ C. The electrolytes
operating temperatures, from room temperature to about 800 °C. There are different materials which
comprise the main ionic conducting phase and an additional phase that is attached to the main phase
can be included in this type of electrolyte. These include perovskites (such as cerate and zirconate)
to improve the electrical, mechanical and thermal properties [33]. As the representative of composite
[65], fluorites (such as doped zirconia, ceria and thoria), pyrochlores (such as calcium doped
electrolytes, alkali metal carbonate (such as LiCO3 ) and oxide (such as LiAlO2 ) and CeO2 doped
lanthanum zirconate) and other materials (including brownmillerite, eulytite and monazite) [33]. The
with Sm2 O3 have shown the expected properties, including oxygen ion, carbonate ion and proton
challenges of this type of electrolyte include their structural stability and the high sintering
conductivity [64]. In addition, Amar et al. [64] have tested mixed Na, K and Li carbonates, in addition
temperature (up to 1700 °C) which is required to achieve a high density. By adopting this kind of
to the LiAlO2 , as the electrolyte. They obtained an ammonia production rate of 2.32 × 10−10 mol/cm2 ·s
solid state electrolyte, the ammonia production rate of 3.1 × 10−9 mol/cm2∙s could be achieved under
at a temperature of about 400 ◦ C. The system with solid electrolytes generally operates in very wide
the temperature of 570 °C, with an efficiency of about 75% [33,66].
operating temperatures, from room temperature to about 800 ◦ C. There are different materials which
can be included in this type of electrolyte. These include perovskites (such as cerate and zirconate) [65],
3.3. Thermochemical Cycle of Ammonia Production
fluorites (such as doped zirconia, ceria and thoria), pyrochlores (such as calcium doped lanthanum
As anand
zirconate) alternative process(including
other materials for ammonia production,eulytite
brownmillerite, a processandemploying
monazite) the
[33].thermochemical
The challenges
cycle
of thishas been
type developedinclude
of electrolyte [67]. The system
their consists
structural of twoand
stability circulated
the highprocesses:
sintering reduction
temperature (nitrogen
(up to
1700 ◦ C) which
activation) and steam‐hydrolysis (ammonia
is required to achieve a high formation).
density. By Both reactions
adopting are summarized
this kind of solid stateaselectrolyte,
follows:
the ammoniaAl2O3production
+ 3C + N2 → rate of 3.1
2 AlN 10−9 mol/cm2 ·s couldΔH°
+ 3× CO be achieved under the temperature of (4)
25 °C = 708.1 kJ/mol
570
◦ C, with an efficiency of about 75% [33,66].

2AlN + 3 H2O → Al2O3 + 2 NH3 ΔH°25 °C = −274.1 kJ/mol (5)

3.3. Thermochemical Cycle of Ammonia Production
Figure 4 shows the schematic diagram of the thermochemical cycle of ammonia production. The
As an alternative process for ammonia production, a process employing the thermochemical
primary energy sources are pre‐treated and converted to carbon before being fed to the
cycle has been developed [67]. The system consists of two circulated processes: reduction (nitrogen
thermochemical cycle process. In the first reduction process (reaction (4)), the AlN is produced
activation) and steam-hydrolysis (ammonia formation). Both reactions are summarized as follows:
through the carbothermal reduction of Al2O3 and nitrogen. This reaction is endothermic and occurs
under a reaction temperature of about 1500 °C. Moreover, in the second reaction, which is steam‐
Al2 O3 + 3C + N2 → 2 AlN + 3 CO ∆H◦ 25 ◦ C = 708.1 kJ/mol (4)
hydrolysis (reaction (5)), the AlN produced in the first reduction process is reacted with steam (H2O)
producing Al2O2AlN 3. The produced Al2O3 from this second reaction
+ 3 H2 O → Al2 O3 + 2 NH3 ∆H◦ 25 ◦ C = is then kJ/mol
−274.1 circulated to the first (5)
reduction process. Detailed reaction kinetics have been analyzed in detail in [68].
Figure
Unlike4theshows the schematic
Haber–Bosch diagram
process, this of the thermochemical
thermochemical cycle cycle
can beofcarried
ammonia outproduction.
at atmosphericThe
primary energy sources are pre-treated and converted to carbon before being fed
pressure and without a catalyst. The process allows independent reaction control for nitrogen to the thermochemical
cycle process.
activation In the first
(reaction (4)) reduction
and ammonia process (reaction(reaction
formation (4)), the AlN
(5)).isFurthermore,
produced through the carbothermal
as could be observed
reduction of Al O and nitrogen. This reaction is endothermic and occurs
from reaction 2(4),3 the system can produce ammonia directly from carbonized material, under a reaction temperature
instead of
of about ◦
1500 C.Therefore,
Moreover, this
in the secondisreaction,
pure hydrogen. system expectedwhich
to beisable
steam-hydrolysis
to reduce the(reaction (5)), the AlN
energy consumption
produced in the first
during ammonia reductionHowever,
production. process isthis
reacted
systemwith steam
has (H2 O) producing
the biggest Al2 O3 .toThe
challenge related its produced
very high
Al O from
operating
2 3 this second reaction is then circulated to the first reduction process.
temperature, leading to limited heat sources and materials. Various ideas have Detailed reaction
been
kinetics
suggested have
forbeen analyzed
the heat in including
supply, detail in [68].
the utilization of concentrated solar heat.

Figure 4. Schematic diagram of the thermochemical cycle of ammonia production.

production.
Energies 2020, 13, 3062 10 of 25

Unlike the Haber–Bosch process, this thermochemical cycle can be carried out at atmospheric
pressure and without a catalyst. The process allows independent reaction control for nitrogen
activation (reaction (4)) and ammonia formation (reaction (5)). Furthermore, as could be observed
from reaction (4), the system can produce ammonia directly from carbonized material, instead of pure
hydrogen. Therefore, this system is expected to be able to reduce the energy consumption during
ammonia production. However, this system has the biggest challenge related to its very high operating
temperature, leading to limited heat sources and materials. Various ideas have been suggested for the
heat supply, including the utilization of concentrated solar heat.
Juangsa and Aziz [69] have developed an integrated system, consisting of nitrogen production,
ammonia production employing the thermochemical cycle and power generation. In their system,
the heat required for reduction is basically covered by heat generated by the combustion of fuel
gases produced during ammonia production. The system can achieve a high total theoretical energy
efficiency of about 69%. In addition, they also stated that the oxidation temperature has a significant
role in the performance of the system.

3.4. Advanced Ammonia Production Systems

Due to increasing concern related to economic and environmental impacts, efforts to propose and
develop an advanced ammonia production system have been carried out intensively. These include
both thermochemical and electrochemical processes.
Cinti et al. [70] have proposed a combined system which consists of solid oxide electrolyser,
nitrogen production with pressure-swing adsorption and Haber–Bosch process. Moreover, the same
group [25] also developed an integrated system covering methane steam reforming and Haber–Bosch
process. They mainly focused on system integration and heat recovery to improve the total energy
efficiency. Furthermore, Aziz et al. [71] have proposed an integrated system for hydrogen conversion
to ammonia with a relatively high total energy efficiency. Their system includes cryogenic nitrogen
separation with a single distillation reactor, the Haber–Bosch process and power generation. The
produced heat during ammonia synthesis, as well as the purged gas (containing a little hydrogen and
ammonia), is recovered and utilized for power generation. In addition, they employed both exergy
recovery and process integration in order to realize high energy efficiency [72].
Other integrated systems for the production of ammonia from various kinds of primary energy
sources have been developed. Nurdiawati et al. [73] have proposed algae-based ammonia production
by integrating algae drying, gasification, chemical looping, ammonia synthesis (the Haber–Bosch
process) and power generation. In their system, the nitrogen separation process is omitted due to
the utilization of nitrogen-rich flue gas from the chemical looping. Their system is able to efficiently
convert the algae to ammonia, with a total energy efficiency of about 64%, including an ammonia
production efficiency of 63%. A different system has also been developed by the same group [74],
with the main difference in hydrothermal gasification and nitrogen production. Another combined
system to convert the agricultural waste from a palm oil mill has also been proposed and evaluated
by Ajiwibowo et al. [75]. In their system, the supercritical water gasification of blended empty fruit
bunch and palm oil mill effluent is combined with syngas chemical looping and Haber–Bosch-based
ammonia synthesis.

4. Ammonia Storage and Transportation

The advantages of ammonia, especially compared to other hydrogen storage methods, include its
well established global distribution network, handling method and regulations covering its storage
and transportation. Ammonia has a higher auto ignition temperature (650 ◦ C) compared to hydrogen
(520 ◦ C), methane (630 ◦ C) and propane (450 ◦ C), leading to its excellent safety. Ammonia is a gas
under atmospheric conditions. Ammonia transportation in a liquid form is generally performed due
to its significantly higher density. The transportation can be performed through pipelines, tank-cars
Energies 2020, 13, 3062 11 of 25

and tanker vessels. In the case of tanker vessels, ammonia is generally cooled down to a temperature
of about −33 ◦ C, allowing the utilization of unpressurized containers [46].
To store ammonia in a liquid condition, which is quite similar that of propane, two methods are
basically adopted. The first method is to increase its pressure while maintaining the temperature at the
ambient level, such as 0.99 MPa at 25 ◦ C. The second method is to decrease the temperature while
maintaining the pressure at the atmospheric level; in this case, ammonia is cooled down to −33.4 ◦ C
at atmospheric pressure [76]. This mild condition is beneficial, as a light and low-cost tank can be
adopted while maintaining its volumetric density. The infrastructure being used for propane can also
be adopted to store liquid ammonia. Therefore, the economic performance for ammonia storage is
considered well established, as well as the regulations for operations and storage.
In order to improve the safety issues during storage and transportation, the storage of ammonia in
a solid form has also been developed [77]. It is basically performed by binding the ammonia in metal
amine complexes (M(NH3 )n Xm ), such as Mg(NH3 )6 Cl2 and Ca(NH3 )8 Cl2 . In case of Mg(NH3 )6 Cl2 , the
reaction occurs as follows:
Mg(NH3 )6 Cl2 → MgCl2 + 6NH3 (6)

These metal ammines have a great gravimetric hydrogen density of about 10 wt% (9.19 and
9.78 wt% for Mg(NH3 )6 Cl2 and Ca(NH3 )8 Cl2 , respectively) [77]. Another benefit of employing metal
ammines to store ammonia is that their apparent toxicity is very low, which is comparable to gasoline
and methanol. For example, Mg(NH3 )6 Cl2 has an IDLH concentration of about 300 ppm, but its
vapor pressure is very low, at 1.4 × 10−3 bar (at 20 ◦ C). The ammonia from the metal ammines can be
released through the desorption process [78]. The desorption of Ca(NH3 )8 Cl2 can be carried out at
a relatively low temperature of about 60 ◦ C, leading to a high ammonia vapor pressure of 0.7 bar at
room temperature.

5. Ammonia Utilization
Currently, ammonia is mainly adopted as an agricultural fertilizer (about 80%), while the remaining
20% is utilized for food production, industrial materials, refrigerants and additives [79]. For energy
harvesting, the utilization of ammonia has not been widely adopted. Figure 5 shows the potential
utilization of ammonia, covering both direct utilization and decomposition to hydrogen. Two main
established technologies to harvest the energy from ammonia include the internal combustion engine
and the fuel cell. The utilization of ammonia as a fuel is expected to realize a clean energy system, as
there is neither CO2 nor SOx emission, nor soot formation [80]. However, further development for a
broader range of energy harvesting from ammonia is demanded.
Efforts to use ammonia in the energy sector have been conducted for several decades. Ammonia
was blended with coal gas as a fuel for the reciprocating engines of buses in the 1940s during World
War II in Belgium [81]. Previously, the patent to utilize blended ammonia, hydrogen and nitrogen as
fuel was also registered in 1938 [82]. In addition, NASA adopted liquid ammonia as the main fuel for
the X-15 hypersonic rocket, blended with liquid oxygen, which was successful in achieving the fastest
speed of Mach 6.7 [83].
The utilization of ammonia faces numerous challenges due to its characteristics. The heating value
of ammonia is significantly lower than that of other hydrocarbons. The narrow equivalence ratio (0.63
to 1.4) and high auto ignition temperature give ammonia low flammability. Ammonia has an adiabatic
flame temperature of 1800 ◦ C, which is lower than hydrogen (2110 ◦ C), methane (1950 ◦ C) and propane
(2000 ◦ C). This leads to lower radiation heat transfer, which is important during combustion and heat
transfer. In addition, it has a low maximum laminar burning velocity (0.07 m/s), which is significantly
lower than hydrogen (2.91 m/s), methane (0.37 m/s) and propane (0.43 m/s).
For energy harvesting, the utilization of ammonia has not been widely adopted. Figure 5 shows the
potential utilization of ammonia, covering both direct utilization and decomposition to hydrogen.
Two main established technologies to harvest the energy from ammonia include the internal
combustion engine and the fuel cell. The utilization of ammonia as a fuel is expected to realize a clean
Energies
energy2020, 13, 3062
system, 12 of 25
as there is neither CO2 nor SOx emission, nor soot formation [80]. However, further
development for a broader range of energy harvesting from ammonia is demanded.

Figure 5.
Figure 5. Potential
Potential utilization
utilization of
of ammonia,
ammonia, including
including direct
direct utilization
utilization and
and decomposition
decomposition to
to hydrogen.
hydrogen.

5.1. Internal Combustion

Efforts to Engine
use ammonia in the energy sector have been conducted for several decades. Ammonia
was blended with coal gas as a fuel for the reciprocating engines of buses in the 1940s during World
The utilization of ammonia as fuel for an internal combustion engine was intensively studied in
War II in Belgium [81]. Previously, the patent to utilize blended ammonia, hydrogen and nitrogen as
the mid-1960s [84,85]. These works confirmed that ammonia has potential as the primary fuel for a
fuel was also registered in 1938 [82]. In addition, NASA adopted liquid ammonia as the main fuel for
spark ignition engine. Starkman et al. [84] found that a maximum theoretical output of about 70% of
the X‐15 hypersonic rocket, blended with liquid oxygen, which was successful in achieving the fastest
that of hydrocarbons could be achieved when gaseous ammonia was injected. In addition, engine
speed of Mach 6.7 [83].
modifications were required to control the fuel flow and spark timing in the case that a conventional
The utilization of ammonia faces numerous challenges due to its characteristics. The heating
spark ignition engine with existing compression ratios was adopted.
value of ammonia is significantly lower than that of other hydrocarbons. The narrow equivalence
The octane number of ammonia is 111 [86]. A thermal efficiency of about 30% and power output
ratio (0.63 to 1.4) and high auto ignition temperature give ammonia low flammability. Ammonia has
of 85% can be achieved by utilizing ammonia in an internal combustion engine. The power output is
limited due to the backfire caused by the lack of water injection and exhaust gas recirculation. Therefore,
the amount of NOx released can be pushed to be significantly lower than that of gasoline. One big
challenge in ammonia combustion is that the minimum ignition energy required by ammonia is about
16 times higher than fossil fuels [87]. Ammonia combustion mainly occurs through the following
reaction:
4 NH3 + 3 O2 → 2 N2 + 6 H2 O ∆H◦ 27 ◦ C = −1.258 kJ/mol (7)

The low combustion rate of ammonia results in inconsistent combustion under low engine loads
and/or high engine speeds [88]. Therefore, combustion promoters (e.g., gasoline, diesel and hydrogen)
are necessary to facilitate more stable combustion. Ryu et al. [89] have conducted a study of blended
gasoline and ammonia in a four-stroke spark-ignition engine. They stated that the appropriate injection
timing for ammonia is in the range of 320–370 before the top dead center (BTDC). The peak cylinder
pressure was slightly lower than that fueled by gasoline alone. Moreover, the use of ammonia led to
the increase of NOx emission and the engine slip phenomenon due to incomplete combustion.
A blend of ammonia and diesel was tested by Reiter and Kong [90] using a four-cylinder
turbocharged diesel engine. They found that, in order to realize a favorable fuel efficiency, ammonia
can be injected in the range of 40–60%, based on the total fuel energy. The increase of ammonia seemed
to increase the amount of emitted NOx , but reduce the amount of soot emission. In addition, Boretti [91]
simulated the ignition performance of mixed diesel and ammonia. His results revealed that ammonia
blending is also able to maintain ignition performance, including power density, power efficiency and
load control. The important thing in this issue was the required injection pressure, which is relatively
high for the ammonia to achieve the expected performance.
Energies 2020, 13, 3062 13 of 25

The blend of ammonia and hydrogen has been studied by Frigo and Gentili [92] using a four
stroke twin cylinder spark ignition engine with a volume of 505 cm3 . They stated that the additional
injection of hydrogen is necessary to improve the ignition and increase the combustion velocity. The
ratio of injected hydrogen depends significantly on the load, while engine speed has less influence.

5.2. Turbine-Based Power Generation

The idea to utilize ammonia for gas turbines was started in mid of 1960s [93], although its practical
adoption as a single fuel for turbines is still limited and has not been widely commercialized. Since
then, research related to the utilization of ammonia as fuel has not been actively performed, except in
research related to NOx formation. Research on the utilization of ammonia as gas turbine fuel was
restarted in the 1990s, especially the utilization of mixed ammonia and hydrogen [94] and ammonia
and natural gas [95].
According to previous research and development projects, there are some challenges when
ammonia is employed as turbine fuel. In addition to slower kinetics and lower combustion temperatures,
the utilization of liquid ammonia as fuel leads to unstable and low combustion efficiency [96]. The
use of a swirler and flame holder can stabilize the combustion and increase its efficiency and reduce
the emitted NOx [97]. The vaporization of liquid ammonia before the combustion and utilization of
additives during combustion, as well as the cracking of molecules, are methods to increase combustion
performance. Moreover, another challenge in the utilization of ammonia as turbine fuel is its relatively
slow chemical reaction rate, leading to a lower laminar burning velocity [98]. Furthermore, as the flow
rate of air is also reduced in order to facilitate sufficient residence time for the reaction, the mixing of
ammonia and air is considered inefficient due to its low Reynolds number [99]. The combustion of
ammonia basically produces no CO2 , which is beneficial in terms of environmental issues. However,
the lack of concentration of CO2 in the flue gas leads to the problems in heat transfer, as CO2 is
considered an excellent heat carrier during combustion and heat transfer. Moreover, the quenching
distance for the mixed ammonia–air under stoichiometric conditions is about 3.5 larger than that of
propane [100].
Keller et al. [101] proposed a combined cycle with two steps of combustion. The first main
combustion uses ammonia as fuel, which is reacted with air, producing nitrogen, water and hydrogen.
These hot gases are then expanded in a gas turbine. In the second step of combustion, which occurs
in a heat recovery steam generator, the hydrogen in the flue gas is reacted with air, adding heat for
steam generation.
A research group at Fukushima Renewable Energy Institute (FREA), Fukushima, Japan, has
succeeded in demonstrating the utilization of ammonia for a micro gas turbine (50 kW) [102]. They
used three different types of fuels, including pure ammonia, mixed ammonia–kerosene and mixed
ammonia–methane [102]. Their developed system adopted a heat regenerative cycle in order to
improve combustion efficiency and flame stability. Their system mainly consists of a vaporizer, gas
compressor, gas turbine and selective catalytic reduction (SCR) unit (Figure 6). SCR was adopted
to reduce the NOx concentration before the flue gas is exhausted into the atmosphere. From the
demonstration test, it was revealed that pure ammonia can realize a combustion efficiency of 89–96%,
while the residual ammonia can be utilized as an additive in the SCR. In addition, it was considered
that the combustor inlet temperature significantly influences the combustion efficiency, as well as the
emissions. Furthermore, when mixed with other fuels, the increase of the ammonia ratio leads to the
increase of the NOx concentration in the flue gas.
reduce the NOx concentration before the flue gas is exhausted into the atmosphere. From the
demonstration test, it was revealed that pure ammonia can realize a combustion efficiency of 89–96%,
while the residual ammonia can be utilized as an additive in the SCR. In addition, it was considered
that the combustor inlet temperature significantly influences the combustion efficiency, as well as the
Energies 13, 3062
2020, Furthermore,
emissions. when mixed with other fuels, the increase of the ammonia ratio leads14
toofthe
25

increase of the NOx concentration in the flue gas.

Figure 6.
Figure 6. Main
Main schematic
schematic diagram of an
diagram of an ammonia-based
ammonia‐based micro
micro gas
gas turbine
turbine (adapted
(adapted from
from [102]).
[102]).

5.3.
5.3. Direct Ammonia Fuel Cell
In the
the case
casethat
thathydrogen
hydrogenneeds
needstotobebereleased
releasedfromfromammonia,
ammonia, thethe
decomposition
decomposition of of
ammonia
ammonia to
hydrogen can be conducted via thermochemical and electrochemical routes
to hydrogen can be conducted via thermochemical and electrochemical routes [103]. However, [103]. However, ammonia
also can bealso
ammonia utilized
can beusing a direct
utilized using fuel cell, without
a direct the
fuel cell, need ofthe
without decomposition or cracking.
need of decomposition or Fuel cells
cracking.
are
Fuelthe technology
cells are the which can generate
technology which can electricity
generatefrom chemical from
electricity resources basedresources
chemical on electrochemical
based on
reactions [104]. Inreactions
electrochemical general, [104].
fuel cells can be categorized
In general, fuel cells canto several types, depending
be categorized to severalon their depending
types, electrolyte
materials, application
on their electrolyte and operating
materials, applicationconditions. These conditions.
and operating categories include alkaline fuel
These categories cellsalkaline
include (AFC),
alkaline
fuel cellsmembrane fuel cells
(AFC), alkaline (AMFC),fuel
membrane phosphoric acid fuel
cells (AMFC), cells (PAFC),
phosphoric acidmolten carbonate
fuel cells (PAFC), fuel cells
molten
(MCFC),
carbonateproton exchange
fuel cells membrane
(MCFC), proton fuel cells (PEMFC),
exchange membrane direct
fuelmethanol fuel cells
cells (PEMFC), (DMFC)
direct and solid
methanol fuel
oxide fuel cellsand
cells (DMFC) (SOFC).
solid Among
oxide fuelthem,
cellsSOFC is considered
(SOFC). Among them, promising
SOFC due to its high promising
is considered energy efficiency,
due to
high fuelenergy
its high flexibility and excellent
efficiency, high fuelenvironmental
flexibility and friendliness
excellent [105]. SOFC operates
environmental at a relatively
friendliness high
[105]. SOFC
operating ◦
operates attemperature; aboutoperating
a relatively high 700 to 1000 C.
temperature; about 700 to 1000 °C.
Although hydrogen is considered to be the most optimal chemical for electricity production via
SOFC, other fuels, including ammonia, have also been investigated, and they have shown relatively
high efficiency [106]. Ammonia can be directly fed as fuel for AFC, AMFC and SOFC. AFC is
the technology which was developed at the early stage of fuel cell technologies. AFC operates at
low temperatures of 50–200 ◦ C using an aqueous potassium hydroxide (KOH) electrolyte with a
concentration of about 30%. The electrodes have a double layer structure, consisting of an active
electrocatalyst layer (an organic mixture of catalyst, carbon black and polytetrafluoroethylene) and a
hydrophobic layer (porous organic layer) [107]. Oxygen is fed at the cathode side, and it has a further
reaction with water, forming hydroxide ions. These ions move to the anode side through the electrolyte
and react with ammonia, producing nitrogen and water. During the reaction, as the produced water
and heat must be removed from the system, the electrolyte is recirculated and the water is evaporated.
The typical electric efficiency of AFC is about 40–45% [108]. One of the problems in conventional
ammonia-fed AFC is the formation and precipitation of carbonate ions. As this formation involves the
hydroxide anion, the amount of hydroxide anions which react with ammonia drops accordingly. This
results in the performance drop of the cell [109]. In order to solve this problem, the anion exchange
membrane-based fuel cell (AMFC) was developed, which is free from cations, such as K+ [110,111]. In
principle, both AFC and AMFC have similar reactions at both cathode and anode, shown as reactions
(8) and (9), respectively.
2 H2 O + O2 + 4 e− → 4 OH− (8)

2 NH3 + 6 OH− → N2 + 6 H2 O + 6 e− (9)

Recently, to further improve the system efficiency, the development of catalysts and new anion
exchange membranes have been carried out [112]. Single metal catalysts, such as Ru, Rh, Pd, Ir and
Pt, and bimetallic catalysts, including Pt-Ru, Pt-Ir/C and Pt-Ni/C, have been investigated in order to
enhance ammonia oxidation activity [113–115].
Compared to both AFC and AMFC, SOFC is considered to have higher energy efficiency [116].
The high reaction temperature of SOFC results in the possibility of ammonia decomposition at the
Energies 2020, 13, 3062 15 of 25

anode; hence, the produced hydrogen can be utilized further for the electrochemical reaction. Farr and
Vayenas [117,118] have studied the utilization of ammonia using a solid electrolyte reactor employing
yttria stabilized zirconia (YSZ) with Pt electrodes. Their research objective was mainly to cogenerate
electricity and nitric oxide (NO) as important chemical feedstock. Moreover, ammonia was first
analyzed as a single fuel for SOFC by Wojcik et al. [119], also using YSZ-based SOFC with Pt electrodes.
They reported that their experiment could achieve a power density of 50 mW/cm2 at 800 ◦ C.
Electrolytes for SOFC can be categorized into proton-conducting (SOFC-H) and
oxygen-ion-conducting (SOFC-O) electrolytes. Oxygen-ion conducting electrolytes are currently
widely adopted. This includes the widely adopted YSZ. Proton-conducting electrolytes have a lower
activation energy for proton transfer, resulting in possible lower operating temperatures compared to
oxygen-ion conducting electrolytes. Therefore, proton-conducting SOFC tends to have higher energy
efficiency [120].
SOFC fed with ammonia as fuel operates based on oxygen ion and proton conducting electrolytes.
The reactions at the anode side occur following the reactions (10) and (11), while one at the cathode
follows the reaction (12).
2 NH3 + 5 O2− → 2 NO + 3 H2 O + 10 e− (10)

2 NH3 + 3 NO → 2.5 N2 + 3 H2 O (11)

0.5 O2 + 2 e− → 2 O2− (12)

Because the diffusion of O2 through the electrolyte is relatively slow, reaction (10) is considered
to be the limiting reaction. As a result, NO is produced and can react with ammonia, producing
nitrogen and water (reaction (11)). Recently, various promising electrolytes have been developed in
order to improve conductivity and increase power density. These include BaCe0.9 Nd0.1 O3−δ [121] and
Ce0.8 Sm0.2 O1.9 [122]. In addition, in order to minimize the formation of nitric oxide, the addition of
doping materials, such as BaCeO3 and BaZrO3 have also been evaluated [123]. The typical electric
efficiency of ammonia-fed SOFC is 50–55% [108].

5.4. Mixing with Other Fuels

In order to advance the combustion performance of ammonia, blending with other enhancers,
such as methane, propane, hydrogen, gasoline and kerosene, is usually adopted [100]. Blending with
hydrogen has been tested by many researchers, and it has a potential to enhance the combustion flame,
as well as to maintain CO2 -free combustion [124–126]. As hydrogen can be produced from ammonia,
from a fuel transportation point of view, this fuel blending is considered practically feasible. Hydrogen
has very high reactivity; therefore, its mixing with ammonia leads to an exponential increase in its
laminar burning velocity compared to pure ammonia. The ammonia and hydrogen mixture has been
evaluated and applied in a spark engine, leading to a robust engine cycle [92]. In addition, the blend
of ammonia and hydrogen has also been tested for gas turbines [94], resulting in an excellent flame
velocity. However, the high diffusivity of hydrogen resulted in a narrow operational envelope. In
addition, they also stated that the high concentration of NOx is caused by the excessive production of
radicals, including OH and O.
Mixing ammonia with other hydrocarbon fuels generally leads to a higher flame velocity, radiation
intensity and rate of heat release, as well as lower CO2 emissions [40]. This blending is also considered
promising in terms of a gentle shift from hydrocarbon to non-carbon-based fuels. Henshaw et al. [127]
studied the effect of ammonia blending on the laminar burning velocity of methane-based combustion.
It was found that increasing the ammonia concentration resulted in a slower laminar burning velocity.
The same tendency has also been stated by Xiao et al. [95], who have simulated the laminar flame
speed. They also found that the increase in the ammonia fraction in the fuel blend led to a negative
effect on the flame speed. It was considered that the increase in the ammonia fraction caused the flame
propagation to be weakened. This slower flame speed was also considered to be due to the decrease of
chemical reactivity following the increase of the ammonia fraction.
Energies 2020, 13, 3062 16 of 25

In addition, Valera-Medina et al. [100] also studied the combustion performance of mixed ammonia
and methane, in terms of flame stability and emission, using a tangential swirl burner. According to
their results, the full premix of fuels before the combustion cannot guarantee an optimum condition for
ammonia combustion, leading to the necessity to find a better method for fuel injection. In addition,
a lower swirl number is necessary to optimize the combustion performance, because a higher swirl
number reduces the residence time, promoting ammonia cracking with a lower oxygen intake and an
increase in radical reactions. The mixture of ammonia and propane has also been researched previously
in [128,129]. Similar results to the above results of the addition of ammonia to methane were obtained.

5.5. Ammonia Decomposition

The hydrogen in ammonia can be released through the decomposition process; therefore, wider
possibilities for hydrogen utilization can be realized. Unlike methanol decomposition, ammonia
decomposition produces no carbon monoxide, resulting in stable hydrogen utilization for PEMFC
and PAFC [130]. PEMFC and PAFC are very sensitive to ammonia due to the acidic nature of their
electrolytes. A hydrogen stream with an ammonia concentration of less than 0.1 ppm is highly expected
for both fuel cells [108]. Both PAFC and PEMFC have an electric efficiency of 40–45% and 40–48%,
respectively. Ammonia decomposition and its subsequent separation and purification processes are
energy-intensive; therefore, efforts to improve their energy efficiency, reliability and scalability are
necessary. Because ammonia decomposition is endothermic and requires high temperatures (>500 ◦ C),
further developments to bring this reaction to a mild temperature region are demanded.
Similar to its synthesis, the decomposition of ammonia is basically a thermo-catalytic reaction.
The decomposition is a stepwise sequence, beginning with ammonia adsorption on the metal and
followed sequentially by ammonia dehydrogenation and the recombinative desorption of nitrogen
and hydrogen [131]. The catalytic activity of catalysts can be observed through their turnover
frequency (TOF), although the decomposition conditions also significantly influence their catalytic
performance [132]. The catalytic activity is significantly influenced by the type of active metal used
as the main catalyst, type of support material, particle size, surface area, dispersion of catalyst and
promoting material [38]. The presence of the additives and the alteration of the support material can
modify the nitrogen desorption step and the catalytic properties of the catalyst [38]. Ganley et al. [133]
have observed the catalytic activity of different single-metal catalysts with Al2 O3 as the support
material and found the activity order to be Pb, Te, Se  Cu < Pd < Cr < Pt  Fe < Ir < Co < Rh < Ni <
Ru. However, due to different ammonia concentrations and types of support material, other studies
mentioned a different catalytic activity order for Pt, Fe, Ni, Co and Pd [134,135].
Although Ru shows the highest catalytic activity, it is expensive, resulting in a high cost of ammonia
decomposition. To solve this problem, efforts to reduce Ru in the catalyst and develop non-Ru catalysts
have been made, while keeping the catalytic activity high. These efforts include the modification of
the primary catalyst component and utilization of promoter and support materials [132]. In addition,
inactive metals can also be used as catalysts with further treatments of surface modifications, promoter
additions and alloying techniques [136].
Numerous promoting materials have been adopted to increase catalytic activity, including K,
Na, Li, Ce, Ba, La and Ca [137]. In addition, K-based compounds, such as KNO3 , KOH, K2 CO3 , KF,
KCl, K2 SO4 and KBr, also have potential as promoting materials [137]. These promoting materials
donate their electrons to the surface of support material, leading to charge balancing during the
decomposition [134]. The promoting material also facilitates intermediate step stabilization due to its
low ionization energy [138]. Moreover, support materials, which are electronically conductive, cheap
and have high surface area, are also expected to improve catalytic activity [132]. Potential support
materials include carbon nanotubes, template SiO2 [139], porous Al2 O3 [140], active carbon, graphitic
carbon and mesoporous carbon [141]. Among the combinations of catalyst and support material, a
catalyst of Ru on carbon nanotubes shows the highest ammonia conversion [38]. This is due to the
Energies 2020, 13, 3062 17 of 25

high dispersion of Ru particles and the inhibition of particle growth of the catalyst [142], resulting in
the stability of the catalyst and high catalytic activity.
Further studies to ensure the comparable results of catalytic decomposition using different
catalysts and conditions are required in order to clarify the optimum decomposition performance. In
real applications, as economic performance is important, catalytic activity is not the only parameter
pursued. However, the stability and lifetime of the materials (including the catalyst, promoters and
support materials) are also crucial factors for consideration, because they significantly influence capital
and running costs, and maintenance.
The hydrogen released by ammonia decomposition needs to be separated and purified, as the
ammonia potentially damages PEMFC [143]. Ammonia poisoning increases both charge-transfer
and diffusion resistances, leading to the decrease of electrochemical performance [143]. Additionally,
the existence of ammonia in the hydrogen gas is disadvantageous due to its toxicity, even in an
ammonia-tolerant energy conversion system (such as AFC). In order to remove the residual ammonia
from the hydrogen gas stream, sorbent materials have been proposed. Miyaoka et al. [144] investigated
the Li exchange type X zeolite to purify the hydrogen gas stream, and obtained 0.01–0.02 ppm of
ammonia at the gas stream outlet (with an inlet concentration of 1000 ppm). Van Hassel et al. [145]
have also developed a metal halide sorbent system, consisting of impregnated super activated carbon
with metal chlorides. They showed that the system has a good cyclic stability. The sorbents can be
regenerated through heating, resulting in the release of ammonia.
Membrane-based separation and purification systems have also been developed recently. This
kind of separation has the benefit of possible simultaneous nitrogen removal; hence, secondary
purifications (e.g., pressure-swing adsorption) can be avoided. Dolan et al. [146] have developed
Pd-coated vanadium membranes in a tubular geometry. The developed membranes showed high
permeability (higher than 3.0 × 10−7 mol/m·s·Pa0.5 at temperatures higher than 320 ◦ C) and robustness.
In addition, as vanadium is a relatively cheap material, this kind of membrane results in a low cost
separation compared to a single Pd-based membrane.

6. Challenges and Recommendations

The biggest challenges related to the realization of a hydrogen-based society are related to
its economy and technological maturity. A hydrogen economy was initially introduced by John
Bockris in 1970 [147], aiming at the massive deployment of hydrogen to substitute current fossil
fuels [148]. Although it is very challenging task, the realization of a hydrogen economy is expected
to strengthen three key pillars in energy sectors, which are energy security, economy [149] and the
environment [150,151]. The target to realize this hydrogen economy has been issued by several
countries, including the USA [5], the European Union [152] and Japan [153].
Wijayanta et al. [154] analyzed the economic performance of different hydrogen storage methods,
including liquid hydrogen, methylcyclohexane and ammonia. According to their study, with the
assumptions that hydrogen is transported from Australia to Japan [155] and the production cost of
hydrogen is 8 JPY/Nm3 -H2 in 2050 [153], the direct utilization of ammonia (no need for decomposition)
is considered to be the most economic, with a predicted final hydrogen price of 21 JPY/Nm3 -H2 in 2050.
However, when a high purity of hydrogen is required, liquid hydrogen is slightly cheaper than the
ammonia with decomposition (24 JPY/Nm3 -H2 compared to 26 JPY/Nm3 -H2 ). Based on the findings
of [153], it is strongly recommended to utilize ammonia directly, whether employing combustion or a
direct ammonia fuel cell. The technologies related to the direct combustion of ammonia need to be
accelerated, so that an optimum combustion performance can be achieved.
Furthermore, related to production and decomposition of ammonia, various technologies are
considered crucial for development. The conventional Haber–Bosch process relies heavily on natural
gas [156]. The adoption of ammonia in the energy sector must be able to facilitate renewable energy
sources; therefore, efficient technologies for the synthesis of ammonia (such as electrochemical and
membrane-based synthesis) are urgently demanded. However, this effort faces a big challenge due
Energies 2020, 13, 3062 18 of 25

to the equilibrium conversion during ammonia decomposition, which is significantly dependent on

temperature, as well being an endothermic reaction. In addition, the rate of ammonia decomposition
also decreases significantly when the reaction reaches its equilibrium [157]. The application of a
membrane to separate the hydrogen is effective in order to avoid this equilibrium limitation [158]. The
development of catalysts in order to increase the decomposition performance, as well as its economy,
is strongly suggested.
In ammonia utilization, a direct ammonia fuel cell is believed to be advantageous, especially in
terms of energy efficiency. However, lowering the temperature in the fuel cell is very challenging
(due to the difficulty in breaking the N–H bonds in ammonia), due to hurdles in finding suitable
electro-catalysts for adoption as the electrode and minimizing the cross-over of ammonia [111]. In the
case of SOFC, the integration of a stable anode, in order to increase the durability of the anode and
electrolyte interface, becomes one of the key issues for the success of ammonia-fed SOFC. The goals of
this include the avoidance of nitride formation and sustaining the local temperature change during its
operation [159].
The integration of several processes, both in the production and utilization sites, is also considered
to be an effective way to improve the total energy efficiency. In the production site, the integration
of ammonia synthesis into the hydrogen production processes, such as gasification, water–gas shift
and steam reformation, is promising for the realization of high total energy efficiency in hydrogen
production and storage [75]. In addition, the technology to lower the temperature during ammonia
decomposition should be accelerated. Integrated ammonia decomposition and power generation in
the utilization site is also an excellent way to utilize ammonia with lower exergy destruction.
Finally, when projecting the adoption of ammonia as a promising secondary energy source, as
well as a hydrogen storage method, the technologies and policies for its development must be in line
with the realization of a CO2 -free energy system. In addition, a massive deployment of renewable
energy and the tremendous variety in the patterns of energy demand lead to a highly flexible and
responsive energy system. Adaptive ammonia production and utilization are considered to be key
technologies in the future.

7. Conclusions
Hydrogen is considered to be a promising secondary energy source (energy carrier) in the future.
However, because of its very low volumetric energy density in a gaseous form under atmospheric
conditions, hydrogen needs to be stored and transported effectively in any form, with high gravimetric
and volumetric hydrogen densities. Among the available technologies, ammonia shows superiorities
over the others, especially in terms of storage, transportation and utilization. In this review, the
production, storage and utilization of ammonia were described. Several important technologies for
each section have been explained. In ammonia production, although the Haber–Bosch process is an
established synthesis technology, electrochemical processes to produce ammonia seem to be promising
for the future, due to their higher energy efficiency. Regarding ammonia storage, ammonia has strong
advantages compared to other hydrogen storage media because it can be stored as a liquid under mild
conditions, similar to propane. Therefore, the storage and transportation infrastructure and regulations
are basically well established. Finally, ammonia utilization covers numerous different technologies,
including internal combustion engines, combustion for turbines and fuel cells. In terms of total
energy efficiency, ammonia fuel cells with direct feeding are believed to be promising. Further studies
correlated to energy-efficient and cost-effective ammonia production and utilization are demanded.
These technologies should be developed in the context of CO2 -free systems. Parallel efforts to accelerate
the adoption of renewable energy, the mutual conversion of hydrogen and ammonia, and the adaptive
management of energy systems are demanded urgently. Furthermore, issues related to the ammonia
economy also become crucial, especially in terms of its adoption into the energy system. Considering
the highly potential characteristics of ammonia, the conversion of renewable energy to ammonia
(renewable ammonia) is considered promising in the future.
Energies 2020, 13, 3062 19 of 25

Author Contributions: Conceptualization, M.A.; resources, M.A., A.T.W., A.B.D.N.; writing—original draft
preparation, M.A., A.T.W., A.B.D.N.; writing—review and editing, M.A., A.T.W., A.B.D.N. All authors have read
and agreed to the published version of the manuscript.
Funding: This work was partially supported by JSPS KAKENHI, Grant Number 19K04211. A.T.W. would
like to acknowledge the support of the World Class Research Program, the Ministry of Research and the
Technology/National Agency for Research and Innovation of the Republic of Indonesia in the fiscal year 2020.
Conflicts of Interest: The authors declare no conflict of interest.

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