E

MARITIME SAFETY COMMITTEE MSC 104/15/10

104th session 2 July 2021
Agenda item 15 Original: ENGLISH
Pre-session public release: ☒

WORK PROGRAMME

Hazard Identification of ships using ammonia as fuel

Submitted by Japan

SUMMARY
Executive summary: This document provides the results of hazard Identification of ships
using ammonia as fuel
Strategic direction, 2 and 3
if applicable:
Output: To be decided
Action to be taken: Paragraph 9
Related document: MSC 104/15/9

Background

1 Utilization of alternative fuels is essential for GHG reduction and ammonia is one of
the promising alternative fuels. Japanese industries have started research and development
(R&D) on ships using ammonia as the main fuel and various R&Ds on ships fitted with
ammonia combustion engines have also been launched in the world.

2 It is, therefore, expected to develop the relevant safety requirements for ships using
ammonia as a fuel, to facilitate the utilization of ammonia as fuel for ships. Japan proposed a
new output to develop non-mandatory guidelines, as an interim measure, for newly built ships
using ammonia as fuel (see MSC 104/15/9).

3 Safety assessment is indispensable to achieve a ship using ammonia as fuel, as such

a ship is developed based on new technologies. Japan carried out a Hazard Identification
(HAZID) study as a part of the safety assessment.

Hazard Identification studies

4 To progress the development of ships using ammonia as fuel, this study, including
the HAZID meeting, was conducted to identify potential hazards of an ammonia fuelled ship.

5 The HAZID study was performed by participants from different areas of expertise to
identify various potential hazards.

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6 As a result of the study, several hazards were identified, some of which were found
to require additional risk control measures. The outline of the HAZID study is set out in the
annex to this document.

Findings

7 The HAZID study revealed that the hazards with a highest Risk Index were as follows:

.1 "ammonia leakage" and "ammonia leakage (piping)" in Fuel tank (S1),

Recirculation system (S2), Liquified fuel supply system (S3) as well as Fuel
valve train (S4); and

.2 "Loss of control" on Valve "D" and Valve "E" in Recirculation system (S2) and
Fuel valve train (S4).

8 Taking into account that the high-risk hazards identified in paragraph 7.2 above also
lead to "ammonia leakage", the most significant hazard will be "ammonia leakage", which may
result in fatality due to toxicity, ensuring the health and safety of seafarers onboard is of utmost
importance. Thus, countermeasures against toxicity on board should be carefully addressed.

Actions requested of the Committee

9 The Committee is invited to consider the result of the HAZID study set out in the annex
to this document when discussing the proposal on new output in document MSC 104/15/9.

***

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ANNEX*

OUTLINE OF THE HAZARD IDENTIFICATION STUDY OF AMMONIA FUELLED SHIPS

1 Purpose

In order to actively contribute to international actions to address the climate change while
ensuring the sustainable growth of maritime transport and related industries, Japan
established the "Shipping Zero Emission Project", in collaboration with the industrial, academic,
and public sectors, in August 2018. The Japan Ship Technology Research Association
(JSTRA) and the Ministry of Land, Infrastructure, Transport and Tourism (MLIT) are taking the
lead in organizing this project and published "Roadmap to Zero Emission from International
Shipping" in March 2020[1]. In order to realize the first-generation zero emission ship being
introduced by 2028, the Roadmap introduces four different concept designs for zero emission
ships and an ammonia fuelled ship is included in the concept designs. Although the ammonia
fuelled ships have only been recently under construction in Japan and several other countries,
there are no safety standards dedicated for ships using ammonia as fuel.

Therefore, it is expected that guidelines be developed, as an IMO instrument, for general use
of ammonia as fuel for ships, to lower the risk of such ships down to the equivalent of the risk
of conventional oil fuelled ships. Taking into account that the ammonia fuelled ships will have
hazards different to hazards of conventional oil fuelled ships, the HAZID (HAZard
IDentification) study including the HAZID meeting, was conducted as a qualitative risk
assessment. The purpose of the HAZID study was to identify significant hazards of
ammonia- fuelled ships, to provide a basis for future discussion on safety measures for such
ships.

2 Object of study and definition

2.1 Object of study

The object of the study is an ammonia-fuelled ship, which is based on a concept of

zero- emission ship in the Roadmap [1]. Figure 2-1 and figure 2-2 show bird's eye views of the
ammonia-fuelled ship. Figure 2-3 shows general arrangements of the ammonia-fuelled ship.
Table 2-1 shows the principal characteristics of the ammonia-fuelled ship. The outline of the
concept design is explained below.

Ship type, hull form and route

Ship types and ship size selected for consideration in the concept design of ammonia-fuelled
ships need to fulfill some conditions. Firstly, they are used in international shipping, which will
keep playing a major role in international logistics, and therefore are to be built in large
numbers. Secondly, they are highly likely to call at ports all over the world, including potential
bunkering points in Europe, the Middle East, Singapore, Australia, Japan, and South America
(such as Chile). In light of these, 80,000 DWT bulk carriers of Panamax class, fulfilling these
conditions, were selected for this concept design of an ammonia-fuelled ship. This concept of
an ammonia-fuelled ship is assumed to travel the route between Japan and Australia.

Ammonia fuel tank

The calorific value of ammonia is low (approx. 44% of that of heavy fuel oil (HFO)). In addition,

*
This annex was prepared by Dr. Y. Nitta, et al. of National Maritime Research Institute, National Institute of
Maritime, Port and Aviation Technology. For further information, please contact: nitta@m.mpat.go.jp

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an ammonia fuel tank needs to be an independent tank with a heat insulating structure.
Therefore, its capacity needs to be two to three times larger than that of the existing HFO
tanks. For this concept design, a cylindrical horizontal IMO Type C tank was selected as a fuel
tank. The upper deck area of the bulk carrier, which was the focus of this concept design, is
occupied mostly by hatch covers and their temporary placing areas. Therefore, space for the
fuel tank is limited unless the cargo hold area is redesigned drastically. In this concept design,
the fuel tank was positioned astern of the accommodation space. The fuel tank capacity and
cruising distance were set based on the consideration on the space necessary for the
installation of fuel handling equipment, deck machinery, funnel and other equipment.

Ammonia fuelled engine

The assumed main engine was a dual fuel engine with an MCR of 9,660 kW x 89.0 rpm. It was
in compliance with the IMO regulations for Tier III NOX control and has a liquid fuel injection
mechanism, which has currently been used for methanol, LPG, and other fuels. As ammonia
fuel is not inflammable, a pilot fuel is necessary to control ignition of ammonia fuel. The engine
assumed for this concept design included a pilot fuel injection valve and had a capability of
maintaining its output using only oil fuel used for the pilot fuel. The supply pressure of the
ammonia into the engine was set at 7 MPa.

Appendix 1 shows physical and chemical properties of ammonia resulted from a bibliographic
survey.

Figure. 2-1 Bird's eye view of the ammonia-fuelled ship

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Figure. 2-2 Bird's eye view from stern side of the ammonia-fuelled ship

Figure. 2-3 General arrangements of the ammonia-fuelled ship

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Table 2-1 Principal characteristics of the ammonia-fuelled ship

Ship principal particulars

Major Dimensions Lpp: 225.5 m x B: 32.26 m x D: 20.10 m
Speed Approx. 14.2 kn
Ship type Bulk carrier
Dead weight ton 81,000
Power system (Future commercialization is assumed)
Propulsion engine Low-speed Dual-Fuel (Ammonia) diesel engine
MAN B&W 6S60ME-C8.5-LGI(A)-HPSCR:
MCR 9,660 kw, NOR 7,052kw
Generator Medium-speed Dual-Fuel (Ammonia)diesel engine
600 kW × 3 sets
Fuel tank
Fuel Ammonia
Total Capacity About 1,550 m3
(for one-way trip between Japan and Australia)
Tank Type IMO Type C horizontal cylindrical tank
(400 kPa (Gage), -33.3°C, steels for low temperature
service)

2.2 Definition and abbreviation

Definitions and abbreviations for this study are indicated below.

Risk: The combination of the frequency and the severity of the

consequence

Severity: The severity in case of an accident or the magnitude of

expected damage

Frequency: The number of occurrences per unit time. In this study, unit
time is defined as per year

Risk index (RI): An indicator that expresses risk using a logarithm. In other
words, it is the sum of the severity index (SI) and the
frequency index (FI)

Severity index (SI): An indicator that expresses severity using a logarithm

Frequency index (FI): An indicator that expresses frequency using a logarithm

Hazard: A potential to threaten human life, health or property or the

environment physical conditions that lead to accidents.
(source of danger)

HAZID: Hazard Identification

FSA guidelines[2]: The guidelines are intended to outline the FSA

methodology as a tool, which may be used in the IMO
rule-making process

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IGF Code: International Code of Safety for Ships using Gases or other
Low-Flashpoint Fuels

IMO: International Maritime Organization

Roadmap: Roadmap to Zero Emission from International Shipping[1]

Fuel preparation room: Any space containing pumps, compressors and/or

vaporizers for fuel preparation purposes

Machinery space: Any space containing an ammonia fuel consumer including

engine

3 Methodology of study

3.1 Structured What-IF Technique (SWIFT)

There are several methods for the HAZID. SWIFT (Structured What If Technique), which is
one example of a What If Study Technique specified in the FSA guidelines, is applied for this
study.

The SWIFT method is a systematic method for hazard identification performed by an expert
meeting. The meeting is brainstorming. In order to identify a hazard by asking questions
starting with "what if?", the questions span topics including deviations in normal operation,
such as operation errors, measurement errors, equipment malfunction, maintenance, utility
failure, loss of containment, emergency operation and external influences. The procedure of
HAZID by SWIFT is as follows:

Step 1 Define the system or process to be analyzed;

Step 2 Identify possible hazards by brainstorming;

Step 3 Assume the consequences;

Step 4 Rank the current risks based on the risk matrix to prioritize the hazards; and

Step 5 Record the discussion.

In this HAZID study, the adequacy of current safety measures and additional safety measures
were not analyzed. This HAZID study was performed by participants from different areas of
expertise to cover all the hazards. The participants in this HAZID study are listed in appendix 2.

3.2 Scope of study

The systems and operational stages within the scope of study are explained below. Systems
and operational stages that are considered to be the same as those of cargo ships using
conventional fuel oil, were excluded from the scope of study.

3.2.1 System

Figure 3-1 and table 3-1 show the systems to be analysed. Figure 3-1 indicates the diagram
of the fuel supply system in ammonia-fuelled ship and table 3-1 shows the list of devices
constituting the fuel supply system. Table 3-2 shows the list of devices constituting systems in
figure 3-1. These diagrams, systems and equipment are derived from the engine system
shown in figure A-3 in appendix 3, which was excerpted from the roadmap, with the addition
of the fuel pump and the service tank connected to the fuel tank. To simplify the study, some
of the equipment has been consolidated or deleted in this HAZID. In addition, the piping

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connecting to each device and vent piping installed in some devices were analysed by
consolidating them for each system.

Figure.3-1 Diagram of the fuel supply system in ammonia-fuelled ship

Table 3-1 List of equipment in the fuel supply system in figure 3-1

ID Equipment ID Equipment
1 Fuel tank 18 Motor "B"
2 Fuel pump 19 Heater/cooler
3 Fuel tank valve 20 Filter
4 Service tank 21 Double block and bleed valve "A"
5 Oil separator 22 Knock-out drum "B"
6 Valve "A" 23 Double block and bleed valve "B"
7 Valve "B" 24 Level switch
8 Gas-liquid separator tank 25 Valve "E"
9 Valve "C" 26 Nitrogen supplier
10 Level transmitter 27 Dry air fan
11 Valve "D" 28 Flow switch
12 Knock-out drum "A" 29 Double wall pipe
13 Low-pressure pump 30 Engine
14 Motor "A" 31 Exhaust pipe
15 Flow meter 32 Flexible joint
16 Buffer tank 33 Exhaust aftertreatment system
17 High-pressure pump

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Table 3-2 List of devices constituting systems in figure 3-1

ID System Equipment
S1 Fuel tank 1, 2, 3, 4
S2 Recirculation system 5, 6, 7, 8, 9, 10, 11,12
S3 Liquified fuel supply system 13, 14, 15, 16, 17, 18, 19, 20
S4 Fuel valve train 21, 22, 23, 24, 25
S5 Nitrogen supply system 26
S6 Double-walled ventilation system 27, 28, 29
S7 Engine and exhaust system 30, 31, 32, 33

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3.2.2 Operation of systems

This section explains details of the operation of the systems to be analyzed. Owing to the
shortage of information, at this stage, on the design and operation of rooms or areas containing
these systems, hazards of such rooms or areas, as well as those of access or connection to
these rooms or areas were excluded from this study.

Fuel tank

During the dual-fuel operation, liquefied ammonia fuel is supplied to the engine by the fuel
supply system from the fuel tank. It is assumed that the fuel supply system is installed on the
weather deck and other systems are arranged under the weather deck. The liquefied ammonia
fuel is transferred by the fuel pump installed in the fuel tank to the service tank through the fuel
tank valve.

Recirculation system

In order to avoid two-phase conditions, a certain amount of liquefied ammonia fuel is

recirculated through the recirculation system. The recirculated liquefied ammonia fuel is
maintained at an appropriate temperature and pressure range [3]. When the dual-fuel operation
is stopped, liquefied ammonia fuel is recovered from the engine through this recirculation
system. Since the recirculated liquefied ammonia fuel contains sealing oil for the injection
valves, an oil separator is installed in the ammonia return line to separate the sealing oil from
the liquefied ammonia fuel. This operation minimized the risk of contaminating the ammonia
fuel storage tank with oil [3]. The gas-liquid separator tank will be installed in front of the
knockout drum "A" to separate purge-derived nitrogen from the recovered liquefied ammonia
fuel before vent. This enables venting at a lower ammonia concentration. It is assumed that
the system will be installed in an area corresponding to the fuel preparation room in the
IGF Code. The flow of the operation is as follows:

.1 the fuel pump installed in the fuel tank transfers liquefied ammonia fuel to the
service tank through the fuel tank valve. The ammonia fuel supplied to the
engine is mostly burned, and the residual fuel passes through the double
block-and-bleed valve "B" and is recovered again in the buffer tank through
the valve "A" and the oil separator;

.2 the nitrogen discharge used for purging is transferred through valve "B" to
the gas-liquid separation tank, where the contained liquefied ammonia fuel
is recovered;

.3 the liquid level in the gas-liquid separation tank is monitored by the liquid
level gauge, and the ammonia fuel is recovered in the buffer tank through
valve "C"; and

.4 the residual gas in the gas-liquid separation tank is exhausted through valve
"D" and knockout drum "A".

Liquified fuel supply system

The liquified fuel supply system contains equipment necessary to supply liquefied ammonia
fuel to the engine at the appropriate temperature, pressure, and other conditions. The liquified
fuel supply system includes high-pressure pumps, heaters, filters, valves, and control systems
to maintain the pressure and temperature of the liquefied ammonia fuel as the engine
consumption changes. It is assumed that the system will be installed in an area corresponding

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to the fuel preparation room in the IGF Code. As the occurrence of collision resulting in a
damage of the buffer tank is deemed unlikely, a hazard owing to such collision was not
considered in this study. The flow of operation is as follows:

.1 The low-pressure pump is operated by the electric motor "A" and transfers
liquefied ammonia fuel from the service tank to the buffer tank;

.2 The flow meter measures the flow rate of liquefied ammonia fuel transferred
to the buffer tank;

.3 The high-pressure pump operated by electric motor "B", transfers liquefied

ammonia fuel from the buffer tank to the engine; and

.4 The ammonia fuel transferred to the engine passes through the filter and the
double block-and-bleed valve "A".

Fuel valve train

The fuel valve train is installed between the engine and the fuel supply system to safely isolate
the engine from the fuel by purging nitrogen in the fuel supply pipe in case of shutdown and
maintenance [3]. When the dual-fuel operation is stopped, the double block-and-bleed valve in
the fuel valve train reduces the pressure and drains the residual ammonia fuel from the engine.
In this study, the double block-and-bleed valve was assumed to be a fail-safe type which can
purge ammonia fuel gas from fuel piping in case of loss of driving power.

Nitrogen supply system

Nitrogen is used to purge the fuel in the engine after dual-fuel operation is stopped, to vent
residual gas before maintenance, and to test the tightness of the system after maintenance [3].
Before every start-up, each system is pressurized with nitrogen to confirm the tightness of the
system. The purging operation is performed when dual-fuel operation is stopped, and the
pressurized nitrogen pushes the ammonia fuel back from the engine to the recirculation system.
The capacity of the nitrogen system should be sufficient to supply a constant flow at a pressure
higher than that of the service tank. Although, it is possible to use dry air or carbon di-oxides
as the media for purging, it was assumed that nitrogen is used as the media for purging in this
study. The operation flow is as follows:

.1 When ammonia fuel is shut off, the fuel supply is shut off by the double
block- and-bleed valve "A" and "B", and nitrogen purging is performed;

.2 Nitrogen gas is supplied to the fuel supply pipe from a nitrogen supplier, and
the residual gas is exhausted through the valve "E" and the knockout drum
"B";

.3 The level switch monitors the amount of residual liquid fuel in the fuel line
and detects that the residual gas has been exhausted. After it is detected
that the residual gas has been exhausted, the nitrogen gas supply is stopped;
and

.4 If a leak from a pipe in the fuel supply system is detected, in addition to the
ammonia fuel shutoff, the nitrogen purge is performed in the relevant pipes,
and the gas is quickly exhausted through the knockout drum "B".

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Double-walled ventilation system

In order to maintain safety in machinery spaces where ammonia fuel consumers are installed,
it is important to detect leaks of liquefied ammonia fuel, prevent diffusion of the leaked gas,
and ventilate the relevant spaces quickly. The ammonia fuel supply piping in the engine area,
therefore, are assumed to be of double wall pipes, and adequate flow of ventilation air is
provided in the annular space between the inner ammonia fuel supply piping and the outer
pipe or duct. The operation flow is as follows:

.1 the ammonia fuel supply pipe to the engine has double-wall piping, and the
annular space in the double-wall piping is constantly ventilated by the dry air
fan; and

.2 the flow rate of the dry air fan is monitored by the flow switch.

Engine and exhaust system

In order to reduce NOX in exhaust from the engine using ammonia fuel, EGR (Exhaust Gas
Recirculation) or SCR (Selective Catalytic Reactor) will be installed in the engine. On the other
hand, a conventional marine SCR system needs urea solution as a reductant for NOX, and a
urea storage tank may be eliminated from an SCR system on an ammonia fuelled ship because
ammonia fuel can be used as the reductant. In this study, hazards owing to conventional fuel
oil operation are not considered, for the reason that such hazards have already been managed
by the existing requirements.

3.2.3 Operational stage

The dual fuel mode using ammonia fuel during navigation was considered in various operation
stages. Because information on the operations of bunkering and gas free was insufficient at
this stage, hazards of these operations were not considered in this study.

3.3 Risk matrix

The significance of each hazard was evaluated by the risk matrix based on the frequency and
the severity. Table 3-4 and table 3-5 show the definitions of Severity Index and Frequency
Index. In addition, table 3-6 indicates the risk matrix based on these FI and SI. These indexes
were deemed similar to those used for the Risk assessment of liquefied hydrogen carriers set
out in document CCC 3/INF.20. As for the toxicity of ammonia, injury and death were taken
into account as the effects on humans. Odor was also considered as the effect on human.
On the other hand, the environmental effects of ammonia were not considered in this study,
for the reason that information on environmental effects and indicators of ammonia were
insufficient. Corrosivity of ammonia on materials was not considered at this stage, as well.

Table 3-4 Severity Index (SI)

Definition S
SI Severity Effects on human (Equivalent
Effects on ship
safety fatalities)
Single fatality or Severe damage (more
3 Severe >1
multiple severe injuries than one week)
Multiple or severe Non-severe ship
2 Significant 0.1
injuries damage (one day)
Local equipment
1 Minor Single or minor injuries 0.01
damage

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Table 3-5 Frequency Index (FI)

F
FI Frequency Definition
(per ship year)
Likely to occur once per one year on more than one
3 Frequent >1
ship
Reasonably Likely to occur once per year in a fleet of 10 ships,
2 10-1
probable i.e. likely to occur a few times during the ship's life
Likely to occur once per year in a fleet of 100 ships,
1 Remote i.e. likely to occur in the total life of several similar 10-2
ships

Table 3-6 Risk matrix

Severity index (SI)

1 2 3
Minor Significant Severe
3 Frequent 4 5 6
Frequency
2 Reasonably probable 3 4 5
index (FI)
1 Remote 2 3 4

4 Result of study

4.1 Result of HAZID

Appendix 4, i.e. HAZID worksheet, shows the detail of the result. Table 4-1 indicates the
identified hazards of which the RIs were 5, i.e. the highest RI in respective systems.

Table 4-1 List of identified Hazard (RI=5)

System ID
S1: Fuel tank S1-6, S1-8, S1-9
S2-3, S2-5, S2-7, S2-9, S2-11, S2-13, S2-14,
S2: Recirculation system
S2-16, S2-18
S3: Liquified fuel supply system S3-2, S3-5, S3-6, S3-8, S3-13, S3-15
S4: Fuel valve train S4-2, S4-5, S4-7, S4-8, S4-9
S5: Nitrogen supply system None
S6: Double-walled ventilation system None
S7: Engine and exhaust system None

This study reveals that the hazards with highest RI were:

.1 "ammonia leakage" and "ammonia leakage (piping)" in Fuel tank (S1),

Recirculation system (S2), Liquified fuel supply system (S3) as well as Fuel
valve train (S4); and

.2 "Loss of control" on Valve "D" and Valve "E" in Recirculation system (S2) and
Fuel valve train (S4).

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4.2 Future tasks

The following issues have not been considered in this HAZID study, owing to the lack of
information, and risks owned by these issues and countermeasures may have to be
considered at a design stage:

.1 hazards in operational stages other than sailing, such as maintenance of

equipment, bunkering and gas free of fuel tanks;

.2 the design, arrangement and operations of rooms and areas containing fuel
tank, recirculation system, liquified fuel supply system, fuel valve train,
nitrogen supply system, double-walled ventilation system or engine and
exhaust system;

.3 detection and removal the ammonia contamination, while the HAZID study
identified hazard of "ammonia contamination" in the heater/cooler in the
liquified fuel supply system;

.4 countermeasures against toxicity such as eye irritation and inhalation

toxicity;

.5 countermeasures against corrosivity to materials; and

.6 the impact on the environment.

5 Summary

This study examines the risks of a ship using ammonia as fuel to identify potential hazards
through simplified HAZID study and HAZID meeting. The result of this study reveals that the
hazards with highest RI are:

.1 "ammonia leakage" and "ammonia leakage (piping)" in Fuel tank (S1),

Recirculation system (S2), Liquified fuel supply system (S3) as well as Fuel
valve train (S4); and

.2 "Loss of control" on Valve "D" and Valve "E" in Recirculation system (S2) and
Fuel valve train (S4).

These hazards should be considered for design, arrangement and operations containing these
systems.

Reference

1 Japan Ship Technology Research Association, 2020, "Roadmap to Zero Emission from
International Shipping", available at: https://www.mlit.go.jp/common/001354314.pdf

2 IMO, "Revised guidelines for formal safety assessment (FSA) for use in the IMO
rule-making process", MSC-MEPC.2/Circ.12, 2013.

3 MAN Energy Solutions, 2020 "MAN B&W two stroke engine operating on ammonia",
5510-0241-01, available at: https://www.man-es.com/marine/products/planning-tools-
and-downloads/technical-papers

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4 National Center for Biotechnology Information, U.S. National Library of Medicine,

available at: https://pubchem.ncbi.nlm.nih.gov/compound/Ammonia

5 Engineering toolbox, available at: https://www.engineeringtoolbox.com/fuels-higher-

calorific-values-d_169.html

6 H. Kobayashi, A. Hayakawa, K.D. K. A. Somarathne, E. C. Okafor, 2019, "Science and

technology of ammonia combustion", Proceedings of the Combustion Institute, 37(1),
pp.109-133, https://doi.org/10.1016/j.proci.2018.09.029

7 C. Morch, A. Bjerre, M. Gottrup, S. Sorenson and J. Schramm, 2011,

"Ammonia/hydrogen mixtures in an SI-engine: Engine performance and analysis of a
proposed fuel system" Fuel, 90 (2), pp.854-864,
https://doi.org/10.1016/j.fuel.2010.09.042

8 INCHEM (database at WHO/IPCS), available at:

http://www.inchem.org/documents/icsc/icsc/eics0414.htm

9 S. McAllister et al., 2011, "Fundamentals of Combustion Processes," Mechanical

Engineering Series, Springer, https://doi.org/10.1007/978-1-4419-7943-8

10 Japan Society of mechanical Engineers, "Thermophysical Properties of Fluids.",

Thermophysical Properties of Fluids, 2000.

11 Y. Niki, 2021, "Reductions in Unburned Ammonia and Nitrous Oxide Emissions From an
Ammonia-Assisted Diesel Engine With Early Timing Diesel Pilot Injection", Journal of
Engineering for Gas Turbines and Power,143(9), pp.091014,
https://doi.org/10.1115/1.4051002

12 ABS, 2020, "Ammonia as Marine Fuel," Sustainability Whitepaper.

13 IMO, Fourth IMO GHG Study 2020 - Full Report.

14 PubChem (database at the National Institutes of Health, US), "compound summary

Ammonia," available at: https://pubchem.ncbi.nlm.nih.gov/compound/222

15 Sigma-Aldrich; Safety Data Sheet for Ammonia (7664-41-7), Product Number: 294993,
Ver.:7.1, Rev. Date: 18. Apr., 2021.

16 New cosmos electric co., ltd., 2016, "Gas Detection and Alarm Systems Product Guide",
available at: https://www.new-cosmos.co.jp/kr/industrial/GA_CTLG_12_06.pdf

17 Ammonia Results - AEGL Program, available at: https://www.epa.gov/aegl/ammonia-

results-aegl-program

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APPENDIX 1

BIBLIOGRAPHIC SURVEY ON USING AMMONIA AS FUEL

This appendix explains the results of bibliographic survey regarding the use of ammonia as
fuel. These results include thermo physical properties, saturated vapor and characteristics
related to safety and utility of ammonia, such as fire, explosion and toxicity.

Thermo physical properties of ammonia

Table A-1 shows the thermo physical properties of ammonia.

Table A-1 Thermo physical properties of Ammonia

No. Properties Ammonia Reference

1 Density (gas) 0.7710 g / L [4]
2 Density (liquid) 0.696 g / cm3 [4]
3 Melting point -77.73°C [4]
4 Boiling point -33.35°C (at 760 mm Hg) [4]
5 Higher heating value 22.5 MJ/kg [4]
18.6 MJ/kg [3], [5]
6 Lower heating value
18.8 MJ/kg [6]
Auto-ignition 630°C [7]
7
temperature 651°C [6]
Minimum auto ignition
8 650°C [5]
temperature
Explosive limits in air: 15-33.6 vol% [7]
9 Flammability limit Equivalence ratio: 0.63-1.40 [5]
Flammability Limits, gas in air: 16-25 vol% [5], [6]
Minimum Ignition Minimum ignition energy: 680 mJ [8]
10
Energy Absolute minimum ignition energy: 8.0 mJ [6]
Maximum laminar burning velocity: 0.07 m/s [5]
11 Flame-velocity
Laminar Flame Speed: 0.15 m/s [6]

Saturated vapour pressure

Figure A-1 shows the saturated vapour pressure of ammonia and figure A-2 indicates the
saturated vapour pressure of nitrogen (N2) and methane (CH4) in comparison to that for NH3[9].
Ammonia is liquefied at a temperature of -33°C under atmospheric pressure (0.1013 MPa).
Ammonia is also liquefied at a temperature of 20°C by pressurizing to a pressure about 0.86
MPa, and at a temperature of 50°C by pressurizing to a pressure about 2.1 MPa. These
properties will be considered for pressure and temperature control of the ammonia fuel storage
tank on board.

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Figure A-1 Saturated vapour pressure of Figure A-2 Saturated vapour pressure of
ammonia N2 and CH4

Characteristics for safety and utility of ammonia

Table A-2 shows characteristics relating to safety and utility of ammonia.

Table A-2 shows characteristics for safety and utility of ammonia

No. characteristics Aspects Reference

1 Toxicity
2 Odour
3 Reaction with metals
Exhaust gas by
4 Exhaust gas compositions includes NOX and N2O
combustion
5 Production
6 Cost
7 Fire extinguisher
8 Explosion proof
Toxicity to humans [7]
Pungent smell [7]
Attacks copper, aluminium, zinc and their alloys [7]
[1], [3], [11]
(In Current) Hydrogen obtained from fossil fuel
[1], [3]
feedstock
(In future) Hydrogen obtained from Renewable
[1], [3]
energy resource
230 USD/ton as of 2019 [12]
660 USD/ ton as of 2030
[13]
660 USD/ ton (32 USD/GJ) as of 2050
Extinguishing media;
Use water spray, alcohol-resistant foam, dry
chemical or carbon dioxide.
Advice for firefighters;
[14], [15]
Wear self-contained breathing apparatus for
firefighting if necessary.
Further information;
Use water spray to cool unopened containers.
Sensor type:
Semiconductor or Electrochemical cell [16]
Group: IIA, Temperature class: T1

Effects of ammonia toxicity on human

Table A-3 summarizes Acute Exposure Guideline Levels (AEGL) for ammonia established by
the Environmental Protection Agency (EPA) in US[17]. The AEGL-1 value was based on a study
in which 2/6 human subjects experienced faint irritation after exposure to ammonia at 30 ppm

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for 10 min. The AEGL-2 values were based on "offensive irritation" to the eyes and respiratory
tract experienced by nonexpert human subjects exposed to 110 ppm of ammonia for two hours.
The AEGL-3 values were based on LC01 values, i.e. non-lethal threshold concentrations in
inhalation toxicity, of 3,317 and 3,374 ppm derived by probit analysis of mouse lethality.

Table A-3 Summary of AEGL Values for Ammonia [17]

10min 30min 60min 4h 8h

AEGL 1 30 30 30 30 30
AEGL 2 220 220 160 110 110
AEGL 3 2700 1600 1100 550 390

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APPENDIX 2

PARTICIPANTS IN THE HAZID STUDY

The HAZID meeting was held on 1 June 2021 and the HAZID study was participated by the
following 52 experts including two chief engineers from 13 entities:

From Mitsubishi Shipbuilding Co., Ltd.:

Two experts in engine room plant design;
An expert in ship hull design;
An expert in ship design; and
An expert in cargo containment system and cargo handling systems;

From Nihon Shipyard Co., Ltd.:

An expert in ship design;

From Mitsui E&S Machinery Co., Ltd.:

Seven experts in engine system;

From IHI Power Systems Co., Ltd.:

Six experts in engine design/development; and
Two experts in engine system;

From Kawasaki Kisen Kaisha, Ltd.:

An expert in engine operation (chief engineer); and
An expert in engine system;

From Mitsui O. S. K. Lines:

Three experts in ship design;
An expert in ship hull design;
An expert in engine operation (chief engineer); and
An expert in engine system;

From NYK Line.:

Two experts in ship hull design;
An expert in ship design; and
An expert in cargo handling systems;

From ITOCHU Corporation.:

Three experts in business development;

From Class NK:

Four experts in international regulation;

From Planning and Design Center for Greener Ships:

An expert in ship design; and
An expert in international regulation;

From Japan Ship Technology Research Association (JSTRA):

An expert in international regulation;

From National Maritime Research Institute (NMRI):

Three experts in engine system;
Two experts in risk assessment; and
An expert in international regulation;

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From Ministry of Land, Infrastructure, Transport and Tourism (MLIT):

Three experts in international regulation.

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APPENDIX 3

DIAGRAM OF A FUEL SUPPLY SYSTEM IN AN AMMONIA-FUELLED SHIP IN ROADMAP

Figure. A-3 Diagram of a fuel supply system in an ammonia-fuelled ship [1]

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APPENDIX 4
HAZID WORKSHEET

Sheet ID: S1, System: Fuel tank system, Phase: Dual fuel mode
Index
ID Hazard Causes Consequences Note
SI FI RI
1 Fuel tank
- Human factors - Damage to the support
- Equipment factors structure
S1-1 Collision - External factors (sea - Ammonia leakage 3 1 4
conditions, traffic) - Fire/explosion
- Other ship - Casualties
- Human factors
- Weld defect
- Impact from falling
objects, etc.
- Sloshing - Interruption of
- Damage to the ammonia fuel supply
support structure - Fire/explosion For Type C tanks, with
- External fire - Low temperature appropriate safety measures
S1-2 Ammonia leakage - Degradation with age embrittlement 3 1 4 against sloshing, problems
- Stress corrosion - Damage to the tank relating to structural strength is
cracking - Injury unlikely.
- Fatigue cracking - Frostbite
- Vibration - Casualties
- Overpressure (failure
of re-liquefaction
process)
- Corrosion
2 Fuel pump
- Human factors
- Equipment factors - Interruption of
- Damage to the ammonia fuel supply
S1-3 Loss of control bearings - Oversupply of ammonia 2 1 3
- Sloshing fuel
- Loss of power - Injury
- Corrosion

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Index
ID Hazard Causes Consequences Note
SI FI RI
- Blockage due to frost
inside the fuel tank
- Relief the pressure
using relief valves of
fuel tank.
- pressurizing of inner
pressure in tank
- Interruption of
- Loss of seal function
ammonia fuel supply
S1-4 Ammonia leakage - Shaft damage due to 3 1 4
- Fire/explosion
sloshing
- Low temperature
embrittlement
- Tank damage
- Injury
- Frostbite
- Casualties
3 Fuel tank valve
- Loss of working medium
- Human factors
- Interruption of
- Equipment factors
ammonia fuel supply
- Damage to the
- Fire/explosion
bearings
- Low temperature "Loss of control" includes Inflow
S1-5 Loss of control - Sloshing 3 1 4
embrittlement and backflow.
- Loss of power
- Tank damage
- Corrosion
- Injury
- Biting of foreign
- Frostbite
substances
- Casualties
- Human factors - Interruption of - "Human factors" includes
- Degradation with age ammonia fuel supply error of operation and
- Lack of gas tightness - Fire/explosion maintenance
of flange - Low temperature - Taking into account the
S1-6 Ammonia leakage 3 2 5
- Defect of gasket embrittlement dissolution of leaked
- Weld defect - Tank damage ammonia into condensed
- Impact from falling - Injury water drain, which may
objects, etc. - Frostbite result in corrosion by

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Index
ID Hazard Causes Consequences Note
SI FI RI
- External fire - Casualties ammonia solution, in case of
- Vibration "ammonia leakage".
- Overpressure (failure
of pressure control)
- Corrosion
4 Service tank
S1-7 Collision Same as S1-1 - Same as S1-1 3 1 4
- Degradation with age
- Lack of gas tightness
of flange
- Defect of gasket
- Weld defect
- Impact from falling
S1-8 Ammonia leakage objects, etc. same as S1-6 3 2 5
- External fire
- Vibration
- Overpressure (failure
of pressure control)
- Corrosion
- Sloshing
Piping
Ammonia leakage
S1-9 same as S1-6 same as S1-6 3 2 5
(piping)
Vent piping
- Ammonia intrusion
through openings in
- Corrosion on the vent
non-hazardous areas or
Improper release of pipping
S1-10 ventilation inlets 3 1 4
ammonia - Improper
- Fire/explosion
arrangement
- Injury
- Casualties

Sheet ID: S2, System: Recirculation system, Phase: Dual fuel mode

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Index
ID Hazard Causes Consequences Note
SI FI RI
5 Oil separators
- Unrecoverable of
unused ammonia fuel
S2-1 Blockage - Foreign substances 1 1 2
- Vaporize of fuel
ammonia
- Lack of maintenance - Sludge generation In case of “Interruption of
(miss to discharge the - Filter blockage ammonia fuel supply”, the
S2-2 Inseparable oil 2 1 3
separated oil, etc.) - Interruption of ammonia engine switched to oil fuel mode
- Corrosion fuel supply automatically.
S2-3 Ammonia leakage same as S1-6 same as S1-6 3 2 5
6 Valve "A"
- Human factors
- Equipment factors
- Loss of drive power - Unrecoverable of
S2-4 Loss of function - Biting of foreign unused ammonia fuel 1 1 2
substances - Pressurize in piping
- Corrosion
- Loss of control
S2-5 Ammonia leakage same as S1-6 same as S1-6 3 2 5
7 Valve "B"
- Human factors - Pressurize in piping
- Equipment factors - Accumulation of
- Loss of drive power residual gas
S2-6 Loss of function - Biting of foreign - Interruption of 2 1 3
substances ammonia fuel supply
- Corrosion - Decrease in engine
- Loss of control output
S2-7 Ammonia leakage same as S1-6 same as S1-6 3 2 5
8 Gas-liquid separator tank
- Human factors - Ammonia leakage
- Equipment factors - Interruption of
S2-8 Collision - External factors (sea ammonia fuel supply 3 1 4
conditions, traffic) - Fire/explosion
- Other ship - Casualties

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Index
ID Hazard Causes Consequences Note
SI FI RI
- Lack of gas tightness
of flange
- Defect of gasket
- Weld defect
- Impact from falling - Fire/explosion
objects, etc. - Low temperature
- Damage to the embrittlement
S2-9 Ammonia leakage support structure - Tank damage 3 2 5
- Loss of function of - Injury
level transmitter - Frostbite
- External fire - Casualties
- Vibration
- Overpressure (failure
of pressure control)
- Corrosion
9 Valve "C"
- Ammonia leakage from
Gas-liquid separator
- Human factors
tank
- Equipment factors
- Fire/explosion
- Loss of drive power
- Low temperature
S2-10 Loss of control - Biting of foreign 3 1 4
embrittlement
substances
- Tank damage
- Loss of function of
- Injury
Level transmitter
- Frostbite
- Casualties
S2-11 Ammonia leakage same as S1-6 same as S1-6 3 2 5

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Index
ID Hazard Causes Consequences Note
SI FI RI
10 Level transmitter
- Ammonia leakage from
Gas-liquid separator - In Start / stop dual fuel mode,
tank Gas-liquid separator tank is
- Human factors - Fire/explosion used.
S2-12 Loss of function - Equipment factors - Low temperature 3 1 4 - The risk can be decreased
- Loss of power embrittlement taking into account for
- Injury capacity design of the knock-
- Frostbite out drum or valve operation.
- Casualties
11 Valve "D"
- Accumulation of
- Human factors residual gas
- Equipment factors - Decrease in engine
- Loss of drive power output
S2-13 Loss of control 3 2 5
- Biting of foreign - Leakage of ammonia
substances fuel
- Corrosion - Ammonia inflow to the
Knock-out drum
S2-14 Ammonia leakage same as S1-6 same as S1-6 3 2 5
12 Knock-out drum "A"
- Fire/explosion
- Loss of control on the - Low temperature
valve "D" embrittlement - Full of capacity includes
S2-15 Ammonia leakage 3 1 4
- Full of capacity - Injury insufficient capacity design.
- pressurizing - Frostbite
- Casualties
Piping
Ammonia leakage
S2-16 same as S1-6 same as S1-6 3 2 5
(piping)
- Interruption of ammonia
Improper fuel
Vaporizing of fuel supply by gas block
S2-17 temperature and 2 1 3
ammonia fuel - Decrease in engine
pressure control
output

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Index
ID Hazard Causes Consequences Note
SI FI RI
- Decrease of fuel supply
- Decrease in engine
Accumulation of Incomplete purge of output
S2-18 3 2 5
nitrogen nitrogen residual gas - Pressurize in piping
- Failure of piping
- Ammonia leakage
Vent piping
- Corrosion to the vent “Human factor” includes
- Ammonia intrusion
pipping “Frequent fuel switching”.
through openings in
- Improper
non-hazardous areas or
Improper release of arrangement
S2-19 ventilation inlets 3 1 4
ammonia - Ammonia emission
- Fire/explosion
more than the design
- Injury
concentration
- Casualties
- Human factor

Sheet ID: S3, System: Fuel supply system, Phase: Dual fuel mode
Index
ID Hazard Causes Consequences Note
SI FI RI
13 Low-pressure pump
- Human factors
- Equipment factors
- Loss of function of the
- Interruption of ammonia
motor "A"
fuel supply
S3-1 Loss of control - Gas suction into the 3 1 4
- Oversupply of ammonia
pump
fuel
- Corrosion
- Blockage due to frost
inside the service tank
S3-2 Ammonia leakage same as S1-6 same as S1-6 3 2 5
14 Motor "A"
- Interruption of ammonia
- Human factors
fuel supply
S3-3 Loss of function - Equipment factors 3 1 4
- Oversupply of ammonia
- Loss of power
fuel

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Index
ID Hazard Causes Consequences Note
SI FI RI
- Interruption of ammonia
- Equipment factors fuel supply This hazard is covered by
S3-4 Ignition/fire - Damaged to the cable - Fire spread to the 3 1 4 countermeasures for
coating by vibration equipment in area or conventional oil fuelled ships.
room
15 Flow meter
S3-5 Ammonia leakage same as S1-6 same as S1-6 3 2 5
16 Buffer tank
- Lack of gas tightness
of flange
- Defect of gasket
- Weld defect
- Impact from falling - Fire/explosion
objects, etc. - Low temperature
- Damage to the embrittlement
S3-6 Ammonia leakage support structure - Tank damage 3 2 5
- Loss of function of - Injury
level transmitter - Frostbite
- External fire - Casualties
- Vibration
- Overpressure (failure
of pressure control)
- Corrosion
17 High-pressure pump
- Human factors
- Equipment factors
- Loss of function of the
- Interruption of ammonia
motor "B"
fuel supply
S3-7 Loss of control - Gas suction into the 3 1 4
- Oversupply of ammonia
pump
fuel
- Corrosion
- Blockage due to frost
inside the service tank
S3-8 Ammonia leakage same as S1-6 same as S1-6 3 2 5

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Index
ID Hazard Causes Consequences Note
SI FI RI
18 Motor "B"
- Interruption of ammonia
- Human factors
fuel supply
S3-9 Loss of function - Equipment factors 3 1 4
- Oversupply of ammonia
- Loss of power
fuel
- Interruption of ammonia
- Equipment factors fuel supply This hazard is covered by
S3-10 Ignition/fire - Damaged to the cable - Fire spread to the 3 1 4 countermeasures for
coating by vibration equipment in area or conventional oil fuelled ships.
room
19 Heater/cooler
- Sludge deposits - Increase of load of
- Loss of maintenance injector
factors - Decrease in engine
S3-11 Loss of function 3 1 4
- Corrosion output
- Loss of power - Interruption of ammonia
- Blockage fuel supply
- Interruption of ammonia
fuel supply
- Fire/explosion
- Low temperature
embrittlement
- There are issues regarding
- Ammonia contamination
S3-12 Ammonia leakage same as S1-6 3 1 4 the detection and removal the
to the refrigerant
ammonia contamination.
- Corrosion to the
refrigerant
- Injury
- Frostbite
- Casualties

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Index
ID Hazard Causes Consequences Note
SI FI RI
20 Filter
- Human factors - Interruption of ammonia
- Blockage due to fuel supply
sludge - Decrease in engine
S3-13 Loss of function 3 2 5
- Failure output due to injector
- Corrosion biting of foreign
- Loss of maintenance substances
S3-14 Ammonia leakage same as S1-6 same as S1-6 3 1 4
Piping
Ammonia
S3-15 same as S1-6 same as S1-6 3 2 5
leakage(piping)

Sheet ID: S4, System: Fuel valve train, Phase: Dual fuel mode
Index Note
ID Hazard Causes Consequences
SI FI RI
21 Double block and bleed valve "A"
- Valve damage due to
- Human factors
liquid sealing
- Equipment factors
- Incomplete purge
- Loss of drive power
S4-1 Loss of control - Fire/explosion in 3 1 4
- Biting of foreign
machinery space
substances
- Injury
- Corrosion
- Casualties
S4-2 Ammonia leakage same as S1-6 same as S1-6 3 2 5
22 Knock-out drum "B"
- Fire/explosion
- Loss of control on the - Low temperature
valve "E" embrittlement - Full of capacity includes
S4-3 Ammonia leakage 3 1 4
- Full of capacity - Injury insufficient capacity design.
- Pressurizing - Frostbite
- Casualties

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Index Note
ID Hazard Causes Consequences
SI FI RI
23 Double block and bleed valve "B"
- Valve damage due to
- Human factors
liquid sealing
- Equipment factors
- Incomplete purge
- Loss of drive power
S4-4 Loss of control - Fire/explosion in 3 1 4
- Biting of foreign
machinery space
substances
- Injury
- Corrosion
- Casualties
S4-5 Ammonia leakage same as S1-6 same as S1-6 3 2 5
24 Level switch
- Incomplete purge
- Corrosion to the engine
by residual ammonia
- Human factors
fuel
S4-6 Loss of function - Equipment factors 3 1 4
- Ammonia leakage in
- Loss of power
machinery space
- Injury
- Casualties
25 Valve "E"
- Accumulation of
- Human factors residual gas
- Equipment factors - Decrease in engine
- Loss of drive power output
S4-7 Loss of control 3 2 5
- Biting of foreign - Leakage of ammonia
substances fuel
- Corrosion - Ammonia inflow to the
Knock-out drum
S4-8 Ammonia leakage same as S1-6 same as S1-6 3 2 5
Piping
Ammonia leakage
S4-9 same as S1-6 same as S1-6 3 2 5
(piping)
- Suffocation
Nitrogen leakage
S4-10 same as S1-6 - Injury 3 1 4
(piping)
- Casualties

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Index Note
ID Hazard Causes Consequences
SI FI RI
Vent piping
- Ammonia intrusion “Human factor” includes
through openings in “Frequent fuel switching”.
non-hazardous areas or
Improper release of
S4-11 - Same as S2-19 ventilation inlets 3 1 4
ammonia
- Fire/explosion
- Injury
- Casualties

Sheet ID: S5, System: Nitrogen supplier system, Phase: Dual fuel mode
Index Note
ID Hazard Causes Consequences
SI FI RI
26 Nitrogen supplier

- Incomplete purge
- Incomplete ventilation in
liquefied fuel supply
- Human factors system
Loss of
- Equipment factors - Ammonia leakage due
S5-1 function/Decrease of 3 1 4
- Loss of drive power to reverse flow
supply pressure
- Loss of maintenance - Fire/explosion in
machinery space
- Injury
- Casualties

S5-2 Nitrogen leakage same as S1-6 - Same as S4-10 3 1 4

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Sheet ID: S6, System: Ventilation system, Phase: Dual fuel mode
Index
ID Hazard Causes Consequences Note
SI FI RI
27 Dry air fan
- Human factors
- Equipment factors
- Loss of power - Incomplete ventilation of
- Corrosion ammonia leakage
- Failure - Fire/explosion in
S6-1 Loss of function 3 1 4
- Loss of maintenance machinery space
- Filter blockage at inlet - Injury
of air - Casualties
- Loss of function of
flow switch
28 Flow switch
- Decrease in air flow
- Blockage due to frost
- Human factors
- Ammonia leakage due
- Equipment factors
to reverse flow
S6-2 Loss of function - Loss of power 3 1 4
- Fire/explosion in
- Corrosion
machinery space
- Loss of maintenance
- Injury
- Casualties
29 Double wall pipe
- Human factors - Fire/explosion in
- Equipment factors machinery space - "Loss of function" includes
S6-3 Loss of function 3 1 4
- Corrosion - Injury outer pipe or duct.
- Loss of maintenance - Casualties

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Sheet ID: S7, System: Engine and Exhaust system, Phase: Dual fuel mode
Index Note
ID Hazard Causes Consequences
SI FI RI
30 Engine
- Human factors
As the following consequences
- Equipment factors - Fire/explosion are similar to those of hazards of
- Over injection - Exhaust gas leakage conventional fuel oil operation,
- Damage to - Ammonia leakage
they were excluded from the
S7-1 Failure instrument mounting - Ammonia contamination 3 1 4
to the coolant
study:
- Stress corrosion
- Injury - Loss of propulsion power,
cracking
- Casualties and
- Loss of maintenance
- Loss power.
- Corrosion
- Human factors
Failure to switch fuel
S7-2 - Equipment factors - Engine stop 2 1 3
oil operation mode
- Instrument failure
- Ammonia leakage
Ammonia leakage to from crank case - Injury
S7-3 3 1 4
the machinery room - Leakage from - Casualties
exhaust pipe
Ammonia - Stress corrosion - Decrease of cooling
S7-4 contamination to the cracking capacity 2 1 3
coolant - Corrosion - Engine stop
31 Exhaust pipe
- Ammonia leakage to the
machinery room
- Exhaust gas leakage to
S7-5 Loss of function same as S1-6 3 1 4
the machinery room
- Injury
- Casualties
32 Flexible joint
- Exhaust gas leakage to
the machinery room
S7-6 Loss of function same as S1-6 3 1 co
- Injury
- Casualties

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Index Note
ID Hazard Causes Consequences
SI FI RI
33 Exhaust aftertreatment system
- The hazards on the piping of
- Exhaust gas leakage to
transferring ammonia to the
- Equipment factors the machinery room
S7-7 Loss of function 3 1 4 exhaust aftertreatment
- Clogging - Injury
system is consolidated to the
- Casualties
fuel piping

___________

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