The Position of Ammonia in Decarbonising Maritime Industry: An Overview and Perspectives: Part I - Johnson Matthey Technology Review
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https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2), 275–290
www.technology.matthey.com
The Position of Ammonia in Decarbonising
Maritime Industry: An Overview and
Perspectives: Part I
Technological advantages and the momentum towards ammonia-propelled
shipping
Tuğçe Ayvalı, S. C. Edman Tsang* 1. Introduction
Wolfson Catalysis Centre, Department of
Chemistry, University of Oxford, Oxford, OX1 Climate change is the most pressing environmental
3QR, UK challenge of our time. Transport, particularly
shipping, has a huge carbon footprint with around
Tim Van Vrijaldenhoven 1 billion tonnes of CO2 equivalent every year
Enviu, Pannekoekstraat 100, 3011 LL, (1). If no further action is taken, then estimates
Rotterdam, The Netherlands from the IMO (2) and European Parliament (3)
suggest that the CO2 emissions from international
*Email: edman.tsang@chem.ox.ac.uk shipping could grow between 50–250% by 2050,
accounting for 17% of global emissions. In 2018,
IMO’s Marine Environment Protection Committee
Shipping, which accounts for 2.6% of global (MEPC) announced an initial strategy on the
carbon dioxide emissions, is urged to find clean reduction of GHG emissions from ships, setting
energy solutions to decarbonise the industry and out a vision to reduce GHG emissions from
achieve the International Maritime Organization international shipping and eventually suspend
(IMO)’s greenhouse gas (GHG) emission targets by them as soon as possible in this century. According
2050. It is generally believed that hydrogen will to their level of ambition, the total annual GHG
play a vital role in enabling the use of renewable emissions (combination of CO2, methane, nitrous
energy sources. However, issues related with oxide and fluorinated gases (4)) from international
hydrogen storage and distribution currently shipping need to be reduced by at least 50%
obstruct its implementation. Alternatively, an before 2050 compared to 2008 (5). In addition,
energy-carrier such as ammonia with its carbon under the revised International Convention for
neutral chemical formula, high energy density and the Prevention of Pollution from Ships (MARPOL)
established production, transportation and storage Annex VI, the global sulfur limit is lowered from
infrastructure could provide a practical short- 3.50% to 0.50% as effective from 1st January
term next generation power solution for maritime 2020 (6). Following IMO’s regulations, many
industry. This paper presents an overview of the initiatives, including some in the United Nations
state-of-the-art and emerging technologies for (UN), European Union (EU) and various national
decarbonising shipping using ammonia as a fuel, governments, are making critical infrastructure
covering general properties of ammonia, the and energy integration decisions to decarbonise the
current production technologies with an emphasis energy and transport sectors until 2050 (7–9). It
on green synthesis methods, onboard storage and is certain that renewable energies are key players
ways to generate power from it. in the global energy transformation to mitigate
275 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
climate change. However, the intermittent nature fuel cell, which are relatively mature technologies
of renewables hinders their integration into the for hydrogen application. Hydrogen not only
electricity distribution grid. A general consensus provides a carbon-free energy solution but also
is that the (excess) electrical energy generated by offers flexibility as most technologies that use fossil
renewable sources should be stored for later use fuels such as natural gas can be adapted to use
on demand to alleviate the impacts of intermittent hydrogen and still provide the same level of service
production. Storage requirements of the electric (12, 13). The benefits of using renewable hydrogen
grid vary widely depending on specific applications are already being recognised commercially for
(10). Most storage technologies fall into five niche applications, including water transport. For
generalised categories, which are mechanical, instance, in February 2020, Enviu, The Netherlands,
electrical, thermal, electrochemical and chemical announced that passengers in Rotterdam will board
energy storage (Figure 1). Among them, chemical a water taxi powered by hydrogen fuel cell in 2021
energy storage, which relies on storing energy in (14). The hydrogen-water taxi is being developed
the chemical bonds of molecules, provides storage by the SWIM consortium (consisting of Enviu,
of high energy density over a long period of time Watertaxi Rotterdam and the (maritime) innovation
and easy transportation from generation to demand companies Flying Fish and ZEPP solutions) that was
sites. initiated as part of Enviu’s zero-emission shipping
It is believed that the chemical energy storage programme Towards Hydrogen-based Renewables
in the form of hydrogen will play a vital role in Used for Ship Transportation (THRUST). When the
enabling the use of renewable energy sources project comes to life, it is going to be the world’s
(for example solar, wind, waves) to reduce CO2 first demonstration for a commercial boat on this
emissions from various industries in the near scale running entirely on a zero-emission fuel. To
future. Particularly, the progressive decrease overcome the infrastructure barrier, parallel to this
in the cost of electrolysers and the increase in project, Enviu is also working on a green hydrogen
carbon taxation may justify large-scale hydrogen tank station. However, powering long distance
production from water via electrolysis, powered by shipping with hydrogen is not practical because
renewable electricity in centralised installations. at scale it must be compressed to around 350 to
This stored energy can then be released again by 700 times atmospheric pressure or cryogenically
using the gas as a fuel in a combustion engine or a cooled to –253°C which is an energy intensive and
Weeks
Chemicals: methane, hydrogen,
ammonia
Days
Flow- Thermomechanical
batteries storage Pumped
ETES hydro
Storage time
Hours CAES
Batteries
ACAES Technology
Aquion
Chemical
NaS, lead acid
Thermal
NaNiCl Flywheel storage Electrochemical
Minutes Li-ion (< 1 MW flywheel, up to 100 MW turbines) Mechanical
Electrical
Super Maturity
capacitor Concept phase
Demonstration
Seconds Early commercial
Commercial
1 kW 100 kW 1 MW 10 MW 100 MW 1000 MW
Power
Fig. 1. Energy storage technologies based on power density and discharge time. ETES = electrothermal
energy storage, CAES = compressed air energy storage, ACAES = adiabatic compressed air energy storage
(11) Copyright Siemens AG
276 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
expensive process. In addition, liquid hydrogen concept design, the first ammonia as fuel design of
requires eight times more storage space than its kind in China (33). MS Color Fantasy, the world’s
heavy fuel oil (HFO) while this is even 30 times largest roll on/roll off (RORO) cruise liner, has also
more for compressed hydrogen (15, 16). As an plans to pilot ammonia as a marine fuel (34). In
alternative, a hydrogen-carrier such as ammonia addition, like Enviu’s THRUST programme from The
with higher volumetric energy density and carbon Netherlands, another non-profit organisation, the
neutral chemical formula has recently been under Mærsk Mc‑Kinney Møller Center for Zero Carbon
investigation as a potential fuel for transport Shipping, was launched in Denmark on 25th June
(17–24). The countries with the world’s top 2020 (35). The organisation aims to bring the best
container ports such as Australia, the UK, Japan minds from science, engineering and business
and Saudi Arabia have recently announced their in order to implement new energy systems and
national zero-emission fuel switch strategies, in technologies for shipping. Although it is not clear
which ammonia plays an important part together yet how the decarbonisation of shipping will be
with hydrogen, and invested millions of US dollars achieved, given the tremendous drive around
for their large scale demonstrations (25–29). The ammonia as a potential zero-carbon emission
steps of major energy players towards alternative fuel, more ammonia-related shipping projects are
zero-carbon emission fuels will certainly have expected to be announced in the near future.
impacts not only in these countries but also beyond. Besides the efforts of individual companies
on developing and expanding their ammonia
powered technologies, recently there has been
1.1 Momentum in Maritime Industry
a tremendous increase in the announcement
Towards Ammonia-Propelled
of consortium projects aiming to demonstrate
Shipping
ammonia-fuelled vessels operating at sea. The
Following the directions, policies and roadmaps of ShipFC consortium could secure €10 million fund
IMO and national regulatory authorities, a number from the EU’s research and innovation programme
of ventures are already underway to test viability Horizon 2020 under its Fuel Cells and Hydrogen
of ammonia in the shipping sector. The engine Joint Undertaking (FCH JU) to deliver the world’s
manufacturers, MAN Energy Solutions (MAN ES, first high-power fuel cell to be powered by green
Germany) and Wärtsilä, Finland, are currently ammonia (36). The ShipFC project is being run
developing two-stroke and four-stroke engines, by a consortium of 14 European companies and
respectively, designed to operate on ammonia and institutions, coordinated by the Norwegian cluster
anticipate that the first ammonia engine could be organisation NCE Maritime CleanTech. The project
in operation in 2024 (30, 31). Both companies aims to demonstrate an offshore vessel, Viking
reported that they had successfully conducted a Energy, which is owned and operated by Eidesvik
preliminary study into ammonia combustibility, AS, Norway, and on contract to energy major
which revealed that slow flame velocity, slower heat Equinor, Norway, powered only with a large 2 MW
release and combustion characteristics of ammonia ammonia fuel cell to sail up to 3000 h annually.
were no obstacle to combustion in these engines One of the main objectives is to ensure that a
(32). Based on their research on combustion large fuel cell can deliver total electric power to
in smaller engines and turbines, the challenges shipboard systems safely and effectively. This is
related to ammonia combustion are determined to the first time an ammonia-powered fuel cell, scaled
be the high nitrogen oxides (NOx) generation, low up from 100 kW to 2 MW, will be installed on a
flammability and low radiation intensity. Further vessel. The design, development and construction
full-scale engine tests will continue to overcome of ammonia-fuelled solid oxide fuel cell (SOFC) will
these challenges in 2021. These tests will serve as be undertaken by Prototech, Norway. Testing will
the platform for the ammonia engine development be executed at the Sustainable Energy Norwegian
at Copenhagen Research Centre of MAN ES and Catapult Centre and the ship-side ammonia system
the Sustainable Energy Catapult Centre’s testing will be supplied by Wärtsilä. It is envisaged that
facilities of Wärtsilä at Stord, Norway. Following the ammonia fuel cell system will be installed in
that, Lloyd’s Register (LR, UK) has granted Viking Energy, UK, in late 2023. The ultimate goal
Approval in Principle to Dalian Shipbuilding is to demonstrate that long-distance, emission-free
Industry Company (DSIC, China) and MAN ES for voyages on big ships are possible.
an ammonia-fuelled 23,000 twenty-foot equivalent Another European based consortium in the Nordic
unit (TEU) ultra-large container ship (ULCS) region was announced in May 2020 (37). The
277 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
Global Maritime Forum has launched The Nordic 1.2 Why Ammonia?
Green Ammonia Powered Ships (NoGAPS), a major
consortium that aims to prove the feasibility of a Recently ammonia has taken considerable
large ammonia-powered deep-sea vessel by 2025. attention and pointed as one of the most promising
Funded by Nordic Innovation, partners of the alternative chemical energy and hydrogen-carriers
project include Danish Ship Finance, shipowner in many technical reports (19, 40), white papers
J. Lauritzen, engine maker MAN ES, Ørsted energy (23, 41) and research articles (18, 22), due to the
group and consultancy group Fürstenberg Maritime following reasons:
Advisory, all from Denmark, along with Oslo-based • Ammonia has an existing infrastructure for
bank DNB, the class society DNV GL, chemical group production, storage and global transport. With
Yara International and the Helsinki-listed Wärtsilä. over 200 million tonnes production per year
In Japan, an industry consortium is collaborating in (42), it is one of the largest chemical industries
a project to develop ships designed to use ammonia in the world
as fuel and go beyond onboard ship technology to • It can be stored as a liquid at relatively low
include “owning and operating the ships, supplying temperature and pressure (cooling to –33°C at
ammonia fuel and developing ammonia supply atmospheric pressure or compressing to 10 bar
facilities.” The participants of the consortium are at room temperature)
Nippon Kaiji Kyokai (ClassNK), Imabari Shipbuilding, • It has high energy density (Table I) which
Mitsui E&S Machinery, MAN ES, Itochu Corporation enables sufficient capacity for long ship voyages
and Itochu Enex (38). In addition, on 6th August without refuelling for weeks (46)
2020, NYK Line, Japan Marine United Corporation • With minor modifications, ammonia can be
and ClassNK signed a joint research and development adopted to be used in internal combustion
(R&D) agreement for the commercialisation of an engines (ICEs) and gas turbines (GTs) in the
ammonia-fuelled ammonia gas carrier (AFAGC) that short term. It has also a strong potential to be
would use ammonia as the main fuel, in addition to used directly in fuel cells in the future
an ammonia floating storage and regasification barge • Ammonia has higher ignition temperature and
(A-FSRB) for offshore bunkering and stable supply of narrower flammability range; therefore, fire
ammonia fuel (39). risk is lower compared to hydrogen
It is likely that more ammonia propelled shipping • It does not contain carbon or sulfur in its
demonstration projects will be announced in chemical formula, thus does not contribute to
the following years. The winners of the contest CO2 and sulfur oxides (SOx) emissions during
will dominate their positions in the value chains utilisation (Table I).
to deploy zero-carbon vessels and bunkering To meet IMO’s targets and ultimately decarbonise
infrastructure across the sector. the maritime sector, vessels powered by zero
Table I List of Selected Marine Fuels and their Characteristics (20, 43–44)
Energy Volumetric CO2 SOx
Storage Storage
a density, energy emission × emission ×
Fuel pressure, temperature,
LHVb, density, 103, kg per 103, kg per
bar °C
MJ kg–1 GJ m–3 tripc tripc
MGO 42.7 36.6 1 rtd 277 0.18
d
HFO 40.4 38.3 1 rt 286 2.12
LNG 50 23.4 1.0 –162 220 0.09
Compressed
120.0 7.5 700 20 0 0
hydrogen
Liquid
120.0 8.5 1 –253 0 0
hydrogen
Liquid
18.6 12.7 1 or 10 –34 or 20 0 0
ammonia
Methanol 19.9 15.8 1 20 254 0.09
a
MGO: marine gas oil; HFO: heavy fuel oil; LNG: liquified natural gas
b
LHV: lower heating value
c
CO2 and SOx emissions were calculated using “THRUST Impact Model” of Enviu (45). The values are based on a single trip from
Piraeus to Rotterdam (5893 km) of a container ship with a size 1000 TEU and engine power of 4609 kW
d
rt: room temperature
278 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
GHG emitting fuels need to be implemented to been identified, summarised and cited in the paper
the international shipping fleet in the early 2020s. for interested readers to explore further.
Ammonia offers several potential advantages over
hydrogen and the conventional marine fuels such as
2. Production of Ammonia
HFO, MGO and LNG. However, several factors such
as sustainable production routes, power generation, Ammonia is currently produced via the Haber-
cost of transition and safety and environmental Bosch process that involves reaction of hydrogen
aspects still need to be considered thoroughly before and nitrogen molecules on a catalyst surface
the implementation and deployment of an ammonia- at a temperature range of 450–600°C and a
powered fleet. The following sections of the paper will pressure of 100–250 bar. Nitrogen is supplied by
cover these aspects. It is also noted that there are many air separation unit and hydrogen is obtained from
valuable studies that have assessed the potential of steam methane reforming (SMR) or, to a lesser
ammonia as an alternative fuel for transport (17–23). extent, coal gasification. This process (so-called
This paper adds to this body of literature by providing ‘brown ammonia’) is energy intensive, consuming
collective, up-to-date knowledge, introducing state- 1% of the world’s total energy production, and
of-the-art and emerging technologies as well as environmentally unfriendly, accounting for 1.8%
identifying the critical research gaps necessary for of global GHG emissions, as hydrogen is supplied
practical application of these technologies. The paper from fossil fuels. From a product lifecycle point
follows an approach to show the picture from a wide- of view, brown ammonia would not offer much
ranging perspective that is of interest particularly environmental benefit if used as a shipping fuel.
for industry without overwhelming with technical For the decarbonisation of ammonia production,
details. Instead, the key and recent studies have three possible methods (Figure 2) are currently
(a) Carbon capture
Natural gas/ and storage (CCS)
coal/
fuel oil
CO2
CH4
Haber- NH3
Reformer/ Water gas Acid gas NH3
Methanation Compression Bosch Cooling
gasifier shift reactor removal storage
process
H2 + N2
Syngas
H2S
Steam/ Steam
air
O2
(b)
H2O H2
Desalination Electrolyser H2 storage
(if required) (if required)
Powered by Haber- NH3
Compressor Bosch Cooling NH3
renewable sources storage
process
Air separation N2 N2 storage
unit (ASU) (if required)
O2
(c)
H2O
H2O NH3
Desalination Electrochemical Ammonia NH3
Electrolyser OR
(if required) cell separation storage
H2
N2
Air separation
unit (ASU)
O2
Fig. 2. (a) Brown (without CCS) and blue (with CCS) ammonia production flowchart; (b) green ammonia
production flowchart; (c) electrochemical ammonia production flowchart
279 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
being considered: (a) conventional Haber-Bosch global warming potential reductions of 54−68%,
production with carbon capture and sequestration when compared to conventional ammonia plants.
(CCS) – so called ‘blue ammonia’; (b) a modified However, scalability of biofuels remains as a
Haber-Bosch process in which hydrogen is supplied challenge. Land used to produce biomass feedstock
by water electrolysis using renewable energies has similar environmental characteristics to that
(wind, solar, tidal wave) – ‘green ammonia’; and (c) of agriculture, thus putting biofuels in competition
direct production of ammonia from water and air in with other land uses and leading to implications
an electrochemical cell – ‘electrochemical ammonia’. for food security, sustainable rural economies and
Designing new ammonia plants with integrated the protection of nature and ecosystems (52).
CCS or retrofitting CCS to conventional plants does Nevertheless, biomass-derived ammonia production
have notable potential and will probably be an might effectively meet the ammonia requirements
intermediate solution in the short term. However, for small territories or isolated applications.
integrating CCS into the existing structure will Another conspicuous alternative pathway for
not only increase the energy consumption, which ammonia production is electrochemical synthesis
is already very high, but will also lead to further where nitrogen is reduced electrocatalytically in the
challenges to find a place to securely store the presence of water or hydrogen. It has been foreseen
captured CO2. The technoeconomic study carried that ammonia production via electrochemical routes
out by Santos and coworkers for the International can save more than 20% of energy consumption
Energy Agency (IEA) Greenhouse Gas R&D as compared to the conventional Haber-Bosch
Programme (47, 48) demonstrates that the method because water can be directly fed into
integration of a CO2 capture plant to an SMR plant the anode chamber of the reactor as a hydrogen
could reduce the CO2 emission between 53% to source without the requirement of initial water
90% whereas the natural gas consumption would electrolysis, and electrochemical reaction can be
increase by 0.46 MJ Nm–3 to 1.41 MJ Nm–3 hydrogen operated at low temperatures and atmospheric
and the amount of surplus electricity exported to pressure. However, none of the electrochemical
the grid by the SMR plant would be reduced. These ammonia synthesis routes has achieved the
changes lead to an increase in the operating cost level of technological maturity required for
of hydrogen production by 18% to 33% compared commercial deployment yet, although a high rate
to the SMR without CCS; thus the levelised (2.4 × 10−8 mol cm−2 s−1 at a maximum current
cost of hydrogen production could increase by efficiency of 4.2%) has recently been achieved
€0.021–€0.051 Nm–3 hydrogen depending on when ammonia was synthesised in molten salt
capture rate and technology selected. Therefore, medium using the electrochemical approach (53).
the use of hydrogen gas generated from water
electrolysis using renewable energies in the Haber-
2.1 Catalysts for Green and Direct
Bosch process for ammonia production would be the
Electrochemical Synthesis of
most convenient route in the medium term because
Ammonia
the process does not contribute to CO2 emission,
electrolysers are already commercially available As described above, green ammonia production
with a scale ranging from kilowatt to megawatt and incorporates two catalytic processes: (a) hydrogen
the cost of electricity from renewable sources is production from water electrolysis; and (b)
declining, making the overall process economically ammonia synthesis from hydrogen and nitrogen via
viable. The use of biomass as a feedstock to provide Haber-Bosch reaction. The high cost of commercial
synthesis gas (syngas) for ammonia production electrolysers arises from the usage of expensive
via Haber-Bosch process might also be regarded noble metals such as platinum and palladium on a
as a green process because the CO2 emitted by carbon support as catalysts in the electrochemical
a biomass-based plant is biogenic which means cells. The catalyst itself has taken up a considerable
that the CO2 released during biomass gasification portion of the total system and capital cost,
and digestion processes is later consumed by especially if there is degradation or corrosion on
biomass-plants as they grow, thus, no extra CO2 the carbon support. Hence, one crucial aspect of
is added to the atmosphere (49). Techno-enviro- the development in hydrogen evolution reaction
economic analyses of ammonia production using (HER) technology is to replace the catalysts with
biomass as feedstock (50, 51) show that the cost earth-abundant alternatives to produce hydrogen
of ammonia produced from biomass feedstock can in a more economical way. Mo et al. (54) has
be competitive with brown ammonia and lead to recently reported that inexpensive silver catalysts,
280 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2) particularly the cubic form of silver nanoparticles, where hydrogen and nitrogen react at 15–25 MPa can clearly exhibit superior HER activity over and 400–450°C using an iron-based catalyst (either platinum at the same metal content by altering magnetite or wurtzite). Low equilibrium single- the rate-determining step in a proton exchange pass conversion (~15%) necessitates the recycle membrane (PEM) electrolyser when practically of unreacted gases, leading to higher energy more negative potential is applied. High activity consumption (58). Compared with commercial was attributed to the weaker Ag−H bond at the iron catalysts, ruthenium-based catalysts offer surface than Pt−H which is more favourable for H advantages in Haber-Bosch reaction because they recombination to form H2. This study is significant to are relatively active at low pressure. Ruthenium rectify the misconception that platinum is always at with a higher electron density in d-orbitals, in the ‘optimal volcano’ position among all monometals assistance with strong electron donor dopants in HER, which has led to an inaccurate description such as alkali metals, can donate electrons into of the surface electrocatalysis under real PEM the anti-bonding orbital of adsorbed nitrogen, conditions at high workload. Beside this scientific facilitating its dissociation, and thus, can work achievement with a monometallic catalyst, start-up under lower pressure. However, ruthenium-based company Hymeth, Denmark, announced in 2019 catalysts have found limited uses in conventional that it would commence the production of HyaeonTM Haber-Bosch processes because they are relatively which is a low temperature and high pressure more expensive and are easily poisoned by carbon electrolyser, at a commercial scale after completing deposition from methane in syngas (59). The tests. The company uses an inexpensive trimetallic electrified Haber-Bosch system, where hydrogen is nickel-copper-iron core-shell electrocatalyst, derived from water, does not contain methane, so possessing high electrochemical activity for both the carbon poisoning effect can be well avoided. oxygen evolution reaction (OER) and hydrogen However it is also known that another surface evolution reaction (HER) (55). Another method of poisoning of ruthenium sites by competitive hydrogen evolution is photocatalytic water splitting. strong hydrogen dissociative adsorption limits This process benefits from direct usage of solar the overall reaction rate. Lately some workers renewable energy without the requirement for the have demonstrated that changing the surface installation of an extra electricity generator such polarity by either decorating terrace sites of as photovoltaic panels or wind turbines to supply ruthenium nanoparticles with Li+ (60) or using power to electrolysers. Although various studies an electrostatically polar MgO(111) in place of have been reported in the past decade (56), no nonpolar MgO as the support (61), can significantly practical application has been implemented yet alleviate the hydrogen poisoning and facilitate an mainly due to low catalytic activities, a narrow range unprecedented ammonia production rate. Another of light absorption and poor quantum efficiencies outstanding study reported by Hattori et al. (62) has (QE) (the measure of the effectiveness of a light demonstrated the ability of ruthenium catalysts to absorbing material to convert incident photons produce ammonia from nitrogen and hydrogen at a into electrons) as a result of fast recombination temperature as low as 50°C. The researchers used of charge carriers. In 2019, Tsang and coworkers a stable electron-donating heterogeneous catalyst, (57) reported a nitrogen-doped titania nanocatalyst cubic CaFH, a solid solution of calcium fluoride and on MgO(111) photocatalyst that has a hydrogen calcium hydride formed at low temperatures to evolution rate of over 11,000 μmol g−1 h−1 in the achieve high performance with an extremely small absence of any sacrificial reagents at 270°C. An activation energy of 20 kJ mol−1 at 50°C, which is exceptional range of QE from 81.8% at 437 nm less than half that for conventional catalysts. to 3.2% at 1000 nm was also stated. High activity If the future green ammonia production via was attributed to formation of oxygen vacancies Haber-Bosch process is carried out in decentralised, upon introducing nitrogen into the titania structure islanded locations in small scale, then hydrogen and prolongation of exciton lifetime over the polar manufactured from an electrolyser at lower MgO(111) surface. The technology readiness level pressure and temperature would require coupling (TRL) of this invention is currently at TRL3–4 but it with an efficient catalyst to achieve high ammonia has a strong potential in the future to harness solar production rate. In this manner, ruthenium stands energy (light and heat) for hydrogen production in out from the other alternatives and high cost may large scale. actually not be a disadvantage. In fact, developing Another energy intensive and costly process in countries, particularly ones located in Africa may ammonia production is the Haber-Bosch process use this opportunity to attract investment as they 281 © 2021 Johnson Matthey
https://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
have high renewable solar energy capacity and rates remain over an order of magnitude away from
resources for platinum group metals. DoE targets, continuous progress is being made
Regarding the electrochemical approach to both in mechanistic understanding of the reaction
synthesise ammonia, there are a number of and in the development of routes to new materials.
potential candidates, which have recently been Finding the ideal combination of mediator, catalyst
demonstrated to be active for this reaction (63–65). and electrolyte components to optimise selectivity
The goal of electrochemical ammonia synthesis, and yield rate, while decreasing energy costs, is
in contrast to electrified Haber-Bosch process, is thought to be the key goal of research in this field
to catalyse the direct reaction of nitrogen with (66) for commercial feasibility.
water to form ammonia at ambient pressure.
The potential elimination of the separation and
2.2 Green Ammonia Demonstration
purification steps for hydrogen when water is used
Plants
as the reductant for nitrogen, along with the input
of electrochemical energy at milder conditions, is Given the fact that green ammonia production from
very attractive. However, the nitrogen molecule water electrolysis followed by Haber-Bosch process
is highly inert towards reduction, much more so would be the most convenient route with current
than the most common electrochemical solvent, technology, several green ammonia demonstration
water. In principle the reaction can proceed under or production plants with a wide range of capacities
ambient conditions, as seen in biology, however have been announced in the past few years.
translating this chemistry into an industrial process Table II summarises these projects including the
while retaining practical rates and efficiencies has key players and their targets.
shown to be challenging. The vast majority of The construction of the first three pilot plants
reports (Figure 3) fall below the targets set by the given in Table II has been completed. They
US Department of Energy (DoE) in the Advanced are currently up and running to carry out R&D
Research Projects Agency-Energy (ARPA-E) toward ammonia synthesis and power generation
Renewable Energy to Fuels Through Utilization from ammonia in a cost-effective way by utilising
of Energy-Dense Liquids (REFUEL) programme renewable energy. The initial test results were
for feasible industrial installations (current reported to be very promising (74–77), paving the
density >300 mA cm–2 and current efficiency way to larger scale, mega projects as announced
>90%, which is equivalent to an effective rate of by several companies from Australia, New Zealand,
9.3 × 10–7 mol cm–2 s–1). Although the present The Netherlands, Spain and Saudi Arabia.
(a) (b)
10–5
3
Current density equivalent, mA cm–2
DoE target 10
10–6
Rate/CE 102
10–7 1
Rate, 10–9 mol cm–2 s–1
No CE
101
Rate, mol cm–2 s–1
10–8
100
10–9
10–1 0.1
10–10
10–2
10–11
10–3 0.01
10–12 Current efficiency, %
10–4
10–13
90 80 70 60 50 40 30 20 10 1 0.1 0.01 10–5
10–14 0.001
0 100 200 300 400 500 600 700 0 10 20 30 40
Temperature, ºC Current efficiency, %
Fig. 3. Overview of rates and current efficiencies for electrochemical ammonia synthesis: (a) rate as
a function of temperature for all reported cells. Colour indicates current efficiency, grey is used where
efficiency data is unavailable; (b) rate as a function of current efficiency for reported aqueous cells around
room temperature. Colour and text indicate principle component of catalyst. Reproduced from (63) with
permission from the Royal Society of Chemistry
282 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
Table II Momentum in Green Ammonia Projects (67–73)
Capacity,
Renewable
Participants Location tonnes Year Purpose
source
per year
University of Morris,
25 Wind 2014 Supply of local fertiliser demand
Minnesota Minnesota, USA
Low temperature/low pressure H-B
FREA, JGC Koriyama,
7 Wind, solar 2018 catalyst optimisation, demonstration of
Corporation Japan
ammonia combustion in gas turbines
Power-to-ammonia-to-power
Siemens Harwell, UK 10 Wind 2018
demonstration unit
Iberdrola, Puertollano, Becoming a European reference for
4000 Solar 2021
Fertiberia Spain sustainable solutions for agriculture
The first small step towards carbon
free fertiliser production by installing
Porsgrunn, 5000 Hydroelectric
Yara 2022 5 MW electrolyser corresponding to
Norway (estimate) grid
1% of the hydrogen production in
Porsgrunn
Demonstration of direct ammonia
Foulum, production from water and air using
Haldor Topsøe 300 Wind 2025
Denmark solid oxide electrolyser without air
separation unit
Production of green ammonia at oil
Air Products,
and gas scale and distribute the green
ACWA Power,
ammonia globally and crack it back
Thyssenkrupp, Saudi Arabia 1.2 × 106 Wind, solar 2025
to ‘carbon-free hydrogen’ at the point
Haldor
of use, supplying hydrogen refuelling
Topsøe, NEOM
stations
Fertiliser production and supply of
OCP Jorf Lasfar 700 Solar TBD
power to marine vessels
Feasibility study (pilot plant scale at
20,000
Antofagasta, 64 MWp solar and 47 MW electrolyser,
Enaex and Solar TBD
Chile full scale at 1030 MWp solar and
350,000
778 MW electrolyser)
Goeree-
Proton
Overflakkee, Part of regional green hydrogen
Ventures, 20,000 Wind, tidal TBD
The economy roadmap
Siemens, Yara
Netherlands
Siemens
Gamesa, Skive, Ammonia production as a way to store
TBD Wind TBD
Energifonden Denmark surplus electricity from wind turbines
Skive
Ballance Agri- The $50 million showcase project as
Kapuni, New 5000
Nutrients, Wind TBD a catalyst for the development of a
Zealand (estimate)
Hiringa Energy sustainable green hydrogen market
Queensland
Nitrates, Determining the technical and
Incitec Pivot, Moura, economic feasibility of producing
20,000 Solar TBD
Wesfarmers Australia renewable ammonia at a commercial
JV, Neoen, scale
Worley
Feasibility study to decarbonise their
Moranbah,
Dyno Nobel 60,000 Solar TBD own nitrogen-based commodity
Australia
production facility
Pilbara, Feasibility study for carbon-free
Yara 25,000 Solar TBD
Australia fertiliser production
Business case demonstration for
H2U, Port Lincoln,
20,000 Wind, solar TBD renewable energy exports (Hydrogen
Thyssenkrupp Australia
Hubs)
283 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
Today, commercial manufacturing of green ammonia effectively within these engines is rather
ammonia is not available anywhere. But, with challenging because ammonia has poor ignition
renewed interest and global drive, it is highly likely that requires high temperature or a secondary fuel
that by 2030, there will be a body of demonstration to initiate the combustion process, low burning
plants that can show the viability of producing velocity (0.015 m s–1) and narrow flammability
ammonia from renewable energy at scale. limit (12–25% air), causing unstable combustion
conditions at very low and high engine speeds and
ammonia slip.
3. Onboard Storage and Power
To date, many studies have been conducted to
Generation from Ammonia
assess the performance and emissions of ammonia
3.1 Onboard Space Requirement propelled combustion engines. Two useful
reviews published by Kobayashi et al. (79) and
With an energy density of 12.7 GJ m–3, ammonia Valera-Medina et al. (18) provide comprehensive
would require a larger volume of space onboard in information about fundamental aspects of
order to deliver the same power as conventional ammonia combustion, the details of the chemistry
marine fuels. For instance, if a HFO fuel tank has of NOx production, processes for reducing NOx and
a volume of 1000 m3, an ammonia fuel tank would validation of several ammonia oxidation kinetics
require 2.75 times more space than that of HFO to models. Results show that ammonia as a sole
provide the same power (30). This might make fuel in a compressed ignition ICE (CI-ICE) is not
ammonia appear unfeasible; however, the space possible due to the high compression ratios needed
requirement for ammonia remains significantly for ignition and combustion. Therefore, co-feeding
smaller compared to other carbon-free options of ammonia with only 5% of a pilot fuel with higher
as the tank volume would be 4117 m3 for liquid cetane number (hydrogen, diesel, methanol,
hydrogen at –253°C; 14,000 m3 for a Tesla Model dimethyl ether) would be enough to facilitate its
3 battery (Tesla, USA) and 120,896 m3 for the combustion. On the other hand, combustion of
battery pack of Corvus Energy, Norway, the marine ammonia as the only fuel might be possible in spark
battery market leader (30). Even carbon-based ignition ICEs (SI-ICEs) (80). In fact, Toyota, Japan,
methanol does not offer significant advantage, filed a patent (81) where it claimed that several
needing a tank volume of 2333 m3. Therefore, the plasma jet igniters arranged inside the combustion
space requirement for ammonia-propelled shipping chamber or plural spark plugs that ignite the
is not found to be unrealistic or inapplicable (24). ammonia at several points can enable ammonia
combustion. Most of the work in the literature
examines the combustion stability and emissions
3.2 Propulsion Systems
from gaseous ammonia blended with carbon-
Two kinds of propulsion systems (direct combustion based fuels or hydrogen in ICEs. It is recognised
and fuel cells) that could use ammonia as a marine that there is generally only a narrow equivalence
fuel stand out regarding the current and emerging dual-fuel ratio where high stability, low emissions
technologies. Figure 4 illustrates the simplified and high temperature can be achieved, leaving a
configuration of these propulsion systems. vast field of research, modelling and testing on
how to improve these parameters to obtain wider
operational ranges and adapt the technology to
3.2.1 Direct Combustion
large marine engines.
Direct usage of ammonia in combustion engines
dates to 1942 when Belgium’s public bus system
3.2.2 Fuel Cell Systems
ground to a halt by a wartime shortage of diesel
(78). As a result, the engine systems of the buses An alternative to generating power from ammonia
were adapted to run with an alternative fuel: liquid in a combustion engine is to use fuel cells, which
ammonia with a small amount of coal gas to help may provide advantages in terms of high thermal
combustion. Although the lifetime of ammonia- efficiencies, less noise and lower emissions of air
powered buses was short, it demonstrated that pollutants. Basically, ammonia can either be used
ammonia could be used as a transport fuel. directly in fuel cells or be used as a hydrogen carrier
Ammonia can be combusted in ICEs or in GTs, where first, a cracker is used to decompose ammonia
both of which are well established as prime into hydrogen and nitrogen and after, hydrogen is
movers in naval vessels. However, burning fed into a fuel cell to generate electricity. Among
284 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
several of the chemical hydrides (82) suggested identified as the most promising for the maritime
for hydrogen storage, such as methanol, formic sector are PEM and SOFCs (23). For use in PEMFCs,
acid and liquid organic hydrogen carriers, liquid either highly active yet cost-effective ammonia
ammonia steps forth with its high gravimetric cracking catalyst operating at low temperature
(17.7 wt%) and volumetric (123 kg m–3) hydrogen regime is required to achieve high purity hydrogen
density, exceeding the 2015 US DoE targets for via complete ammonia conversion in a single gas
hydrogen storage (9.0 wt% hydrogen content, stream pass or gas purifier equipment needs to
81 kg m–3 volumetric capacity). It also benefits be installed which would involve additional costs
from the absence of carbon oxides (COx) emissions together with mass, space and energy demand
associated with hydrogen as a fuel in fuel cells. onboard. Compared to PEM, SOFC is much more
Ammonia can be directly used in alkaline fuel promising for maritime application as ammonia can
cells (AFCs) and SOFCs, whereas PEM fuel cells be used directly instead of separating hydrogen
(PEMFCs) require high purity hydrogen (>99.5%) from it first. However, further research is required
as the catalyst is poisoned in the presence of to optimise the operation conditions, increase the
small amount of ammonia (22, 83). The fuel cells system lifetime and scale-up.
NH3 (gas)
Air Electric power
NH3 NOx
(liquid) H2 (gas) Internal combustion (gas) Selective N2
NH3 (gas) Ammonia
NH3 storage Evaporator engine or gas catalytic
cracker H2O
turbine reduction
Heat
NH3 (gas)
Direct combustion
Electric power
NH3 (gas)
NH3 NOx
(liquid) NH3 Internal combustion (gas) Exhaust N2
NH3 storage Evaporator engine or gas
(gas) purification
turbine H2O
Support
fuel storage Air
tank
NH3 (gas)
Air
NH3 (liquid) NH3 (gas) H2 Purifier H2 (gas) Alkaline or
Evaporator Ammonia
NH3 storage cracker PEM fuel cells H2O
Unreacted (if required)
NH3
NH3 (gas)
Fuel cells
Electric power Low quality
heat
NH3 (gas)
Air
NH3
(liquid) NH3 (gas) N2
Evaporator Solid oxide
NH3 storage
fuel cells H2O
Electric power High quality
heat
Fig. 4. Possible propulsion systems process diagrams using ammonia as a marine fuel
285 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
3.2.3 Catalytic Processes Involved a Phase One feasibility study for its Ammonia
in Ammonia to Power to Green Hydrogen Project (89). In the report,
lithium imide catalyst is highlighted as a low-cost
For the onboard usage of ammonia, two propulsion and high performance state-of-the-art catalyst.
systems are considered as stated in previous Phase Two of this project will be related to further
sections. Because of the low flammability of development of the cracker to raise the TRL of a
ammonia, generally a second fuel with higher lithium imide based ammonia cracker catalyst from
cetane number needs to be fed into the combustion TRL4 to TRL6/7 by demonstrating and validating
engine to start ignition and combust ammonia. the feasibility of the technology developed.
One of the fuel options to assist the combustion Compared to PEMFCs, SOFCs offer direct usage of
might be hydrogen due to its high flammability ammonia without the requirement of precracking
and environmental friendliness. As ammonia is a and gas purification processes. With an operation
hydrogen carrier, extra storage space for hydrogen temperature in the 700–1000°C range, ammonia
may not be necessary. Instead, ammonia can cracking can be thermally integrated within the fuel
be cracked to its forming molecules, nitrogen cell stack. The key challenges with ammonia SOFCs
and hydrogen, catalytically onboard. Ammonia in the literature were thought to be the durability
decomposition is not new, and has long been of the anode/electrolyte interface and a risk for
used in industry. The process is endothermic; NOx emission (83). However, research conducted
however, the equilibrium conversion shows at the University of Perugia, Italy, with the support
diminishing returns for temperatures above 400°C. of Enviu indicated that the degradation rate of a
Inexpensive catalysts such as nickel or iron might SOFC operating at 750°C during 100 h of testing
be suitable to crack ammonia onboard at low with ammonia is equivalent to one operating under
temperatures (using the heat generated from the the same conditions with hydrogen (90). Moreover,
combustion engine) as only 5% hydrogen in the analysis shows that there was no nitrification of the
gas stream would be enough to combust ammonia anode, which practically means no NOx formation.
effectively. However, for PEMFC applications, This study showed that at operative temperature
high purity hydrogen (>99.5%) is required since there is no risk of anode degradation when
a large quantity of ammonia leads to catalyst applying ammonia. In addition, the off-gas analysis
poisoning in fuel cells. Although nickel catalysts showed no presence of ammonia, indicating that
can achieve this conversion, more than 900°C is a complete decomposition of ammonia occurred
required. The reviews reported by us (59) and by inside the cell. With these tests a system efficiency
others (84, 85) present a comprehensive list of of 57.5% at a power density of 0.39 W cm–2 has
ammonia decomposition catalysts and the activity been achieved. SOFCs are now becoming an
values under their optimum working conditions. important field of R&D. The translation of these
Among all these reported materials, ruthenium scientific findings to technology will pave the way
catalysts appear to be the most promising to their commercialisation and deployment in the
candidates due to their high ammonia conversion near future.
rates at lower temperatures. Considering the high
costs and scarcity of noble metals, a low cost but
3.3 Technology Status of Ammonia
highly active catalyst working at temperatures
Powered Ship Propulsion Systems
aligned with those of the PEMFCs, in the range of
150–200°C, is needed for the practical conversion of So far, none of these propulsion technologies
ammonia under industrial conditions. For instance, for ammonia has yet been commercialised and
a core-shell catalyst preparation approach might be deployed for shipping but a design study for such
followed to decrease the amount of any expensive a vessel was recently published by de Vries (43).
metal component and replace it at the core with a The author reviewed all options covering ICE,
cheaper metal in the working catalysts. With this PEMFC, AFC and SOFC for marine applications. It
method, the stability of catalysts against metal has been concluded that the SOFC scores best in
sintering may also be improved. The alkali amide efficiency but lacks power density, load response
(–NH2) (86) and imide (–NH) materials (87, 88) are capability and is still too expensive. The ICE is
also emerging as promising inexpensive catalysts second in efficiency and thus more efficient than
for ammonia decomposition at mild conditions. the PEMFC and the AFC (in case these are operated
The UK’s Department for Business, Energy and close to maximum power). Additionally, the ICE
Industrial Strategy (BEIS) recently published is less expensive, more robust with acceptable
286 © 2021 Johnson Mattheyhttps://doi.org/10.1595/205651321X16043240667033 Johnson Matthey Technol. Rev., 2021, 65, (2)
power density and load response. Based on these Emissions from Harder-to-Abate Sectors’, Energy
comparisons, the ICE has been identified as the Transitions Commission, London, UK, November,
best option for maritime applications at the current 2018
technology status but SOFCs are considered to 8. “Energy Roadmap 2050”, European Union,
have a lot of potential in the future. Luxembourg, 2012, 24 pp
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used for ammonia (30, 91). However, when 19 pp
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