Hydrogen storage

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 Hydrogen storage
Content

1. Hydrogen storage options

2. Compressed hydrogen storage
2.1 Types of compressed gaseous hydrogen (CGH2) storage vessels
2.2 On-board hydrogen storage
2.3 Pressure relief devices (TPRDs)
2.4 Consequences of catastrophic failure of high-pressure hydrogen storage
2.5 Fire resistance rating (FRR) of hydrogen tanks
2.6 Safety strategies for inherently safer high-pressure hydrogen storage
2.7 CGH2 storage: potential hazards and safety issues
3. Interaction of hydrogen with different materials (metallic and polymeric)
4. Limitation of hydrogen permeation
5. Liquefied and cryo-compressed hydrogen storage
6. Solid storage of hydrogen
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 Hydrogen storage
Objectives of the lecture (1/2)

1. Understand how hydrogen is stored and appreciate the challenges associated with different types
of storages;
2. Distinguish between various storage options of hydrogen: compressed gas, liquefied and storage
in solids;
3. Recognise different types of storage vessels currently in use to store compressed hydrogen;
4. Name the main components of on-board hydrogen storage;
5. Explain the working principle of a TPRD fitted onto hydrogen storage and make a comparison with
TPRDs used in storage of other fuels (CNG, LPG, etc.);
6. Learn the main aspects of storage tank testing in general and bonfire test protocols in particular;
7. Explain the causes, which may lead to a catastrophic failure of high-pressure hydrogen storage
vessel and its consequences;
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 Hydrogen storage
Objectives of the lecture (2/2)

8. Identify factors affecting the fire-resistance rating of hydrogen tanks;

9. Define safety strategies for inherently safer compressed hydrogen storage;
10. Understand the main safety and technical issues associated with compressed hydrogen storage;
11. Explain the mechanisms of hydrogen interaction with metallic and polymeric materials;
12. Establish effect of hydrogen embrittlement on safety of hydrogen storage systems;
13. Define the hydrogen permeation phenomena;
14. Point out the safe permeation rate for hydrogen storages on-board of passenger cars and buses;
15. Identify safety concerns associated with liquefied hydrogen storage and storage of hydrogen in
various solid materials.

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 Hydrogen storage
Hydrogen density

• Hydrogen is the lightest gas with a low

normal density 0.09 g/L (at 288 K and 1
bar)
• Hydrogen has a high energy content
by weight and low energy content by
volume
• Volumetric and gravimetric densities
describe hydrogen storage
• Challenge – to develop safe, reliable,
compact , light-weight, and cost-
effective hydrogen storage technology
Source: Andreas Zuttel, H2FC Technical School, 2014

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 Hydrogen storage
Volumetric and gravimetric capacities

• Volumetric and gravimetric

capacities/densities are used to describe
gas storage approaches. Hydrogen
research activities moving towards
increasing both capacities.
• Cryo-compressed storage of hydrogen is
the only technology that is close to revised
2015 DOE targets for volumetric and
gravimetric efficiency
Source: Risø Energy Report 3, 2004

Problem: difficult to store large quantities of hydrogen under atmospheric pressure and ambient temperature
without taking up significant amount of space (need for large tanks). Critical for use in vehicles: size and
weight constraints for achieving sufficient driving range (500+ km). To increase volumetric density gaseous
hydrogen (GH2) is compressed to high pressures (p).

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 Hydrogen storage
Compressed gaseous (CGH2) storage

• For industrial or laboratory uses

CGH2 stored in metal cylinders at
pressures of 15-20 MPa.
• For on-board storage CGH2
typically compressed to 35 (buses)
or 70 MPa (cars).
• The cylinders are designed for
maximum working pressure with a
Three different pressure levels at refuelling station :
minimum wall thickness.
low-pressure storage (‘cigar’ tanks, p=4.5 MPa)
• At refuelling stations CGH2
medium-pressure storage (a group of cylinders, p=20-50 MPa)
pressurised in stages (up to 100
MPa). high-pressure storage (composite cylinders, p=70-100 MPa)
Example: Linde hydrogen refuelling station
Note: 1MPa =10 bar; 1MPa = 106 Pa https://www.youtube.com/watch?v=Pjh639S2dek
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 Hydrogen storage
Nominal Working Pressure

❖ Nominal Working Pressure (NWP) is a gauge pressure, which characterises typical operation
of a system. For CGH2 containers NWP is a settled pressure of compressed gas in fully filled
container at a uniform temperature of 15 °C (definition).
❖ FC vehicles onboard hydrogen is typically stored at NWP of 35 MPa or 70 MPa, with maximum
fuelling pressures of 125% of NWP (43.8 MPa or 87.5 MPa, respectively).
❖ Most commonly hydrogen is dispensed at pressures up to 125% of NWP
❖ During the normal (re-)fuelling process, the pressure inside the container may rise up to 25%
above the NWP as adiabatic compression of the gas causes heating within the containers. As the
container cools down after refuelling, the pressure drops. By definition, the settled pressure of the
system will be equal to the NWP when the container is at 15 °C.

Source: GTR, Proposal for a global technical regulation (gtr) on hydrogen fuelled vehicles, 2013
G. Parks, R. Boyd, J. Cornish, R. Remick. Hydrogen station compression, storage, and dispensing technical status and costs. NREL independent review panel, 2014
summary report

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 Hydrogen storage
Tanks for CGH2 storage

4 types of vessels
Type I: made of metal
Type II: metallic vessel hoop-wrapped with fibre resin composite
Type III: metallic liners fully-wrapped with fibre resin composite In 2014 the first prototype of type V tank was
Type IV: polymeric liner fully wrapped with fibre resin composite produced. It is an all-composite vessel without a liner.
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 Hydrogen storage
Materials for CGH2 storage vessels

Hydrogen is prone to leakage due the small size of its molecules!

Storage tanks have at least two layers. The thickness of the walls depends on the
pressure to be applied.
Materials:
• for liners - metals (steel or aluminium), plastics (high density polyethylene
(HDPE) or polyamide), etc.
• for wrapping – thermoset or thermoplastic resin, aramid fibres, etc.
• Metals must not allow hydrogen permeation or be subjected to hydrogen
embrittlement (especially when their use involve extensive pressure and temperature cycling)
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 Hydrogen storage
Type I and II vessels

Type I vessel Type II vessel

• seamless containers made of • seamless metallic vessels;
steel or aluminium; • hoop-wrapped with fibre resin;
• very heavy vessels with thick • very heavy vessels;
walls; • can withstand pressures up to
• steels susceptible to hydrogen 45-80 MPa;
embrittlement; • used as high pressures buffers
• designed for pressures not higher at hydrogen filling stations;
than 25MPa; • cost is competitive due to a
• used in natural gas vehicles; low number of fibres
• relatively cheap storage option for
stationary applications

Not suitable for automotive applications due to the weight and volume constrains
Sources: Barthelemy, H (2007). Teaching materials of the 2nd European Summer School on Hydrogen Safety, 30 July-8 August 2007, Belfast, UK.

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 Hydrogen storage
Type III and IV vessels
Containers are lighter in weight; thinner walls compared to type I and II vessels

Type III Type IV vessel

vessel

• Non-metallic (plastic) liners wrapped with fibre/polymer matrix

• Metallic bosses are in place for shut-off valves installation
• Fibre wrapping provides strength required
• Seamless or welded aluminium liners • Although the cylinders are lighter than all-metal liners they are more expensive
• Fully wrapped with fibre resin composite • NWP = 70 MPa
• Less affected by hydrogen embrittlement • Disadvantage: hydrogen permeation through the liner

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 Hydrogen storage
On-board hydrogen storage
The key functions: 35MPa Type III
• to receive hydrogen during fuelling; Aluminum Alloy Liner
• to contain hydrogen until needed;
• to release hydrogen to FC system for use in powering the vehicle.

Fuel Cell
Carbon Fiber
Reinforced
35 MPa Compressed Hydrogen Tanks Polymer (CFRP)
Type III : Fully wrapped composite tanks with metal liners
Type IV : Fully wrapped composite tanks with plastic liners

Source: Tomioka, J (2011) The 4th International Conference on Hydrogen Safety September 18th, 2011

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 Hydrogen storage
On-board hydrogen storage tanks (1/2)

• FC car (up to 6 kg hydrogen):

Source: Honda Emergency Response Guide. Honda Fuel Cell Vehicle

It could be more than one tank (e.g. Toyota Mirai FCV has two 70 MPa tanks)
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 Hydrogen storage
On-board hydrogen storage tanks (2/2)

• FC bus (typically 25 kg hydrogen, 600 L hydrogen at 70 MPa)

• Several tanks located on the bus roof
• Advantages of FC buses compared to the conventional ones are lower concentration of
greenhouse gases; increased energy efficiency and a quieter operation.

Source: Tim Mays, H2FC Technical School , 2014 Photos: courtesy of National HFC FR training, USA

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 Hydrogen storage
Type IV tank for GH2 storage

Cross section of Quantum hydrogen storage tank wall

Source: http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/04_warner_quantum.pdf

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 Hydrogen storage
Composite type IV tank
• Permeation is specific to
Typical components: type IV vessels.
• container/vessel Permeation rate should not
• check valve be higher than 6 ml/hr/L (at
20oC) – EU regulation
• shut-off valve
• Hydrogen diffusion through
• thermally activated polymeric material
pressure release
• Hydrogen accumulates
device (TPRD)
between the liner and
CFRP forming a ‘blister’.
• May cause partial or full
collapse of the liner (if p of
accumulated hydrogen becomes
higher than internal pressure the
liner)
Source: http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/04_warner_quantum.pdf • Development of special
polymers
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 Hydrogen storage
Issues with CGH2 storage
Technical issues
• Large volumes of tanks required
5 kg - estimated amount of hydrogen an FC car needs for 500-km driving range
The densities of gaseous hydrogen at room temperature: 23 g/L (at 35MPa, room temp.); 39 g/L (at 70MPa, room
temp.). To store 5 kg of hydrogen on-board of a FCH vehicle minimum volumes of 217 L and 128 L will be
required to accommodate 35 MPa and 70 MPa, respectively. In reality the volumes should be even larger.
• Heavy weights (e.g. 66 kg when empty). The weight of hydrogen stored is ca. 1% of a tank weight . It drops
even lower than 1% at pressures above 35MPa (higher pressures need thicker cylinder walls).
• High costs
Safety issues
• Loss of containment/rupture
• Interaction of hydrogen with materials used for liners (metals or plastics)
• Heating effects during refilling
• Filling orientation
Source: Klebanoff, L (Ed) (2012). Hydrogen storage technology: Materials and applications. Boca Raton: CRC Press. Taylor&Francis.

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 Hydrogen storage
Pressure relief devices (PRDs)

• In the event of a fire, thermally activated pressure relief device (TPRD) provides a controlled
release of the CGH2 from a high pressure storage container before its walls are weakened by high
temperatures leading to a hazardous rupture.
• TPRDs vent the entire contents of the container rapidly. They do not reseal or allow re-
pressurization of the container.
• Storage containers and TPRDs that have been subjected to a fire are expected to be removed from
service and destroyed [1].
• PRDs are designed according to codes and standards. PRDs should be manufactured, installed,
operated, maintained, inspected, and repaired according to laws and rules of local jurisdictions [2].
• On-board hydrogen storage must be fitted with PRDs/TPRDs according to the European
Commission Regulation (EU) No 406/2010.
Sources:
[1] GTR, Proposal for a global technical regulation (gtr) on hydrogen fuelled vehicles, 2013.
[2] Malek M.A. Pressure relief devices ASME and API code simplified. McGraw Hill, New York, 2006 .

European Hydrogen Train the Trainer

Source: Programme for Responders
H2BestPractices.
 Hydrogen storage
How TPRDs work

• PRDs are designed to open when pressure or

temperature reaches a certain limit. TPRDs open if
temperature is above 108-110oC.
• Hydrogen tanks should be protected with non-
reclosing TPRDs
• A glass bulb PRD: bulb is hollow and contains
liquid. Upon heating the bulb breaks down; frees
the poppet to move to the left. This opens the O-
ring seal and vents the gas through the radial ports.
• A bayonet PRD: upon reaching its triggering
temperature (ca.124 °C) the trigger melts and
allows the ball bearing to move and release the
spring, which punctures the safety disk with a
bayonet. The content of the storage tanks is
PRD before (left) and after activation (right)
released through the hollow bayonet. A bayonet PRD used in CNG buses (Mirada) Glass bulb PRD (Rotarex)

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 Hydrogen storage
Why and how TPRDs fail

TPRD failures:
Type 1: a TPRD fails to vent properly.
Type 2: a premature activation of a TPRD.
Type 3: a TPRD fails to be activated.
• TPRDs can be blocked during incident/accident.
• TPRDs can become corroded or otherwise damaged such that they
relieve pressure when they should not be
Useful link: http://depts.washington.edu/vehfire/begin.html
CNG bus on fire videos:
https://www.youtube.com/watch?v=vHf2o9oVY24
https://www.youtube.com/watch?v=IvuDiZkHJUo

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 Hydrogen storage
Global Technical Regulations (GTR) 2013

• A PRD shall be a non-reclosing and a thermally activated device.

• A PRD shall be directly installed into the opening of a container, or at least one container in a
container assembly, or into an opening in a valve assembled into the container, in such a manner that it
shall discharge the hydrogen into an atmospheric outlet that vents to the outside of the vehicle.
• It shall not be possible to isolate the TPRD from the container protected by the PRD, due to the normal
operation or failure of another component.
• The hydrogen gas discharge from TPRD shall not be directed:
➢ towards exposed electrical terminals, exposed electrical switches or other ignition sources;
➢ into or towards the vehicle passenger or luggage compartments;
➢ into or towards any vehicle wheel housing;
➢ forward from the vehicle, or horizontally from the back or sides of the vehicle.

Source: GTR, Proposal for a global technical regulation (gtr) on hydrogen fuelled vehicles, 2013.

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 Hydrogen storage
Testing of hydrogen tanks

GTR 2013
Tests applicable to all types of tanks:
• Hydrostatic burst test: the pressure at which the tank bursts, typically more than
twice of the working pressure.
• Leak-before-break test: the fuel tank shall fail by leakage or shall exceed the
number of filling cycles (11,250)
• Bonfire test: the fuel tank shall vent through the non-reclosing TPRD; the fuel tank
shall not fail when exposed to a bonfire of 20 minutes duration.
• Penetration test: the fuel tank shall not rupture when an armour piercing bullet or
impactor with a diameter of 7.62 mm or greater fully penetrates its wall.

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 Hydrogen storage
RCS relevant to fire tests
Table 1. Selected RCS applicable to fire tests of high pressure hydrogen storage tanks
RCS Title Country Year

SAE J2578 General fuel cell vehicle safety U.S. 2002

2009 re-published
SAE J2579 Fuel systems in fuel cell and other hydrogen vehicles U.S. 2008
2009 re-published
JARI S001 Technical standard for containers of compressed hydrogen vehicle fuel devices Japan 2004

ISO 15869 Gaseous hydrogen and hydrogen blends - Land vehicle fuel tanks (Technical International 2009
Specification)

EU regulation Implementing EC Regulation 79/2009 on type-approval of hydrogen-powered EU 2010

406/2010 motor vehicles

GTR 2013 Proposal for a Global Technical Regulation (GTR) on hydrogen and fuel cell International 2013
vehicles. (ECE/TRANS/WP. 29/GRSP/2013/41).
GTR Number 13 The United Nations Economic Commission for Europe Global Technical North America, 2017
Regulation (GTR) Number 13 (Global Technical Regulation on Hydrogen and Japan, Korea, EU
Fuel Cell Vehicles)

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 Hydrogen storage
GTR fire tests

➢ A hydrogen storage container fitted with a TPRD, a check valve, a

shut-off valve and any additional features including vent line(s) and
vent line covering(s) and any shielding affixed directly to the container
(such as thermal wraps and coverings/barriers over TPRD(s)).
➢ A hydrogen storage system is pressurized to a nominal working
pressure (NWP) and exposed to fire.
➢ A high-pressure container shall vent through a TPRD in a controlled
manner without a hazardous rupture.

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 Hydrogen storage
Fire test procedure (1/3)
Table 2. A summary of conditions for a test started as a localized fire (GTR, 2013)
Test method Method 1, generic installation test (without protective devices, only thermal shielding)
Method 2 for specific vehicle installation (includes protective devices and other
vehicle components)
Pressure in the container 100% of nominal working pressure (NWP)
Medium in the container Compressed hydrogen/compressed air can be used if agreed in certain
regions/countries
Distance from the container to the fire 100 mm
source
Fire source LPG burners configured to produce uniform minimum temperature
Fire source length 1.65 m
Fire source width Encompass the entire diameter (width) of the storage system
Number and the location of Minimum 5 TCs covering the length of the container up to 1.65 m maximum. At least
thermocouples (TCs) 2 TCs are in localized area and at least 3 TCs equally spaced no more than 0.5 m
apart in the remaining area
Position of TCs 25±10mm from outside surface of the container along its longitudinal axis
Additional TCs At TPRD sensing point or at any other location
Wind shields To ensure uniform heating
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 Hydrogen storage
Fire test procedure (2/3)
Table 2. A summary of conditions for a test started as a localized fire (contd.) (GTR, 2013)

Length and width of localised fire 250±50 mm and the width encompasses the entire diameter of the tank
Localized fire exposure area Area furthest from TPRD(s) – generic installation (Method 1)
The most vulnerable area should be identified for specific vehicle installation (Method 2).
This area, furthest from TPRDs, positioned directly over the fire source
Tmin of TCs in localized area From 600 to 900 °C - from 3 to 10 mins of fire exposure
Tmax of TCs in localized area From 800 to 1100 °C - from 12mins until release of hydrogen via TPRD(s)
Start of engulfing fire Main burner is ignited at 10 mins of the test and fire source is extended to 1.65 m. After
12 mins of exposure the temperature should be increased to at least 800 °C
Tmin of TCs within engulfing region 800 °C – from 12 mins until release of hydrogen via TPRD(s)
Duration of the test Test continues until the system vents through a TPRD and the pressure falls to less
than 1 MPa. The venting shall be continuous (without interruption), and a storage
system shall not rupture. An additional release through a leakage (not including
release through a TPRD) that results in a flame with length greater than 0.5 m beyond
the perimeter of the applied flame shall not occur.

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 Hydrogen storage
Fire test procedure (3/3)

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 Hydrogen storage
Engulfing fire test: GTR (1/2)

Table 3. A position of a container above the fire

Container length Number of Position of a container
TPRDs

≤1.65 m 1 Horizontal; centrally above the fire source

>1.65 m 1 PRD at one end Horizontal; above the fire source that
of a container commences at the opposite end of a container

>1.65 m >1 PRD along the Horizontal; centrally above the fire source,
length of a centre of which is located midway between
container those PRDs that are separated by the greatest
horizontal distance

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 Hydrogen storage
Engulfing fire test: GTR (2/2)
Table 4. A summary of conditions for engulfing fire test
Medium in the container Compressed hydrogen at 100% of NWP
Fire source length 1.65 m
Number of TCs Minimum 3 TCs suspended in the flame approx. 25 mm below the bottom of the container
Distance to the fire source 100 mm
Metallic shielding To prevent direct flame impingement on a container valves, fittings, or PRDs. Metallic
shielding should not be in direct contact with fittings
Fire protection of TCs Metallic shielding or TCs may be inserted into blocks of metal measuring less than 25
mm×25mm×25mm
Tmin of TCs Within 5 minutes after fire is ignited, an average flame temperature should not be less than
590 °C (determined by the average of two TCs recording the highest temperatures over 60
seconds interval)
Measurements Temperatures of TCs and a container pressure shall be recorded every 30 seconds during
the test
Duration of the test Until container fully vents (pressure falls below 0.7MPa)

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 Hydrogen storage
Blow-down of hydrogen storage tank
Nomogram for hydrogen tank blowdown to 0.2 MPa
100 MPa 70 MPa 35 MPa 20 MPa

106 10
6
10
6
106 0.3

Release hole size (mm)

0.5
5 5
Blowdown time in seconds (s)
10
5
10
5
10 10 1.0
2.0
4
4
10
4
10 4
10 3.0
10
5.0
3
10
3
10
3
103 10 10.0
20.0
2 2
10
2
10 2
10 10

1 1
10
1
101 10 10

0 0
10
0
10
0
10 10

10
-1
10
-1
10
-1
10-1
10 100 1000 10000
Tank volume (L)

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 Hydrogen storage
Fire test protocols: GTR - 2013
Localized fire region Time period, min Engulfing fire region (outside the localized fire region)
Action Ignite burners 0-1 No burner operation
T min Not specified - Not specified
T max <900oC - Not specified

Action Increase temperature and stabilize fire for start 1-3 No burner operation
of localized fire exposure - Not specified
T min >300oC - Not specified
T max <900oC

Action Localized fire exposure continues 3-10 No burner operation

Tmin 1-minute rolling average >600oC Not specified
T max 1-minute rolling average <900oC Not specified

Action Increase temperature 10-11 Main burner ignited at 10 mins

T min 1-minute rolling average >600oC Not specified
T max 1-minute rolling average <1100oC Not specified

Action Increase temperature and stabilize fire for start 11-12 Increase temperature and stabilize fire for start of engulfing fire
of engulfing fire exposure exposure
T min 1-minute rolling average >600oC > 300oC
T max 1-minute rolling average <1100oC <1100oC

Action Engulfing fire exposure continues 12 – end of the test Engulfing fire exposure continues
T min 1-minute rolling average >800oC 1-minute rolling average >800oC
T max 1-minute rolling average <1100oC 1-minute rolling average <1100oC

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 Hydrogen storage
Results of the fire test
➢ The arrangement of the fire should be recorded in sufficient detail to ensure the rate of heat input to the
test article is reproducible.
➢ The results include:
➢ the elapsed time from ignition of the fire to the start of venting through the TPRD(s), and
➢ the maximum pressure and time of evacuation until a pressure of less than 1MPa/0.7MPa is reached.
➢ TCs temperatures and a container pressure should be recorded at intervals of every 10 sec/30 sec or less
during the test.
➢ Compliance to thermal requirements begins 1 minute after entering the period with constant minimum and
maximum limits and is based on a 1- minute rolling average of each thermocouple.
➢ Any failure to maintain specified minimum or maximum temperatures invalidates the test results.
➢ Any failure or inconsistency of fire source should invalidate the test results.
GTR should include fire test without a TPRD and provide information on Fire Resistance Rating (FRR) for
public and firemen safety.
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 Hydrogen storage
Effects of fire on high pressure storage tanks
• Maximum temperatures measured on the composite surface: (750-850 oC)
• The cylinders rupture in a fire, where TPRD is absent or does not activate.
• The polymer resin disappeared but the carbon fibres did not burn.
• The release of hydrogen through an orifice with a diameter of 0.5 mm and opening within 90 seconds
prevented the studied 36 L cylinder from bursting.
Engulfing bonfire test A wall of the composite tank after the fire Results of the leak test after the fire

Source: Ruban, S, et al (2012). Fire risk on high-pressure full composite cylinders for automotive applications. International Journal of Hydrogen Energy, Vol. 37, pp. 17630-17638.

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 Hydrogen storage
Catastrophic failure of storage tank in a fire (1/2)

• Experiment sponsored by the Motor Vehicle Fire Research Institute (MVFRI) and operated
by Southwest Research Institute (SWRI), USA [1].

• Storage pressure about 35 MPa, no pressure relief device (PRD), propane burner
(perforated piping in a wind-barrier pan). Only 1.64 kg of hydrogen (Zalosh, 2007) [2].

• Type IV tank tests: 72.4 L (LxD=84x41 cm) stand-alone tank, high-density polyethylene
liner, carbon fibre structural layer, and fiberglass outer layer. Heat Release rate (HRR)= 370
kW, P=34.3 MPa. Fire resistance rating (FRR) = 6 min 27 s

• Type III tank tests: 88 L tank under a typical SUV (Sports Utility Vehicle, LxW=4.5x1.8
m), 28 cm above the ground. HRR=265 kW (GTR 2013 issue), P=31.8 MPa. FRR = 12
min 18 s.
Sources: [1] Weyandt, N (2006). Vehicle bonfire to induce catastrophic failure of a 5000-psig hydrogen cylinder installed on a typical SUV, Motor Vehicle Fire Research Institute. Report. December, 2006. Available from:
www.mvfri.org
[2] Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th Seminar on Fire and Explosion Hazard, Edinburgh, UK, 23-27 April 2007, pp. 2154-2161.

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 Hydrogen storage
Catastrophic failure of storage tank in a fire (2/2)

Test observations:
• The internal cylinder temperature and pressure increased only
marginally (due to a low thermal conductivity of CFRP) from 27oC to
39oC and from 34.5 MPa to 35.7 MPa during final period between 6 min and
6 min 27 s of fire exposure, which culminated in a catastrophic rupture of
type IV tank.
• Burning of tank composite layers started in 45 s (Type IV) and 20 s (Type
III) – black soot appearance.
• Flame penetrated the vehicle (SUV) interior after about 4 minutes of
exposure fire.

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 Hydrogen storage
Bonfire test: type IV tank (no TPRD)

“Fire resistance” is 1-6 minutes.

No combustion contribution to
the blast.

https://www.youtube.com/watch?v=n-
Jh5kPdvTE&list=PLlphoM9ggM3Rf-
Npmdq0S3WrCSpx0U4SL&index=9
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 Hydrogen storage
Blast waves (TPRD blocked)

Type IV (stand-alone). Measured peak pressures varied from 300 kPa at 1.9 m, to 41 kPa at 6.5 m. The
highest pressures were in a direction perpendicular to the tank longitudinal axis.

Type III (under SUV). 140 kPa at 1.2 m, 12 kPa at 15 m. Blast pressures were higher in a direction parallel to
the fuel tank longitudinal axis.

Please note: pressure effects on people (Barry, 2003):

- 10.3-20 kPa - people are knocked down;
- 13.8 kPa - possible fatality by being projected against obstacles;
- 34 kPa - eardrum rupture;
- 35 kPa - 15% probability of fatality;
- 54 kPa - fatal head injury;
> 83 kPa - severe injury or death (about 5 m) http://www.mvfri.org/Contracts/Final%20Reports/CNGandH2VehicleFuelTankPaper.pdf.

Note: Energy stored in a tank is proportional to PxV (larger tanks has more hazardous potential through the
blast wave in case of rupture)
Source: Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th Seminar on Fire and Explosion Hazard, Edinburgh, UK, 23-27 April 2007, pp. 2154-2161.

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Fireball
• Type IV: a fireball is 7.7 m in diameter (45 ms after thank rupture). Fireball is lifted in 1 s (see Figs. below, left).
• Type III: a fireball is 24 m in diameter.
• Simple correlation (Zalosh, 2007) gives 9.4 m for 1.64 kg of hydrogen.
• Fireball duration is about 4.5 s in both cases (IR video), and twice less by high-speed visible range cameras.
• Correlation (Zalosh, 2007) gives 0.6 s duration (does not work!)
• Heat flux (Type III) measured at a distance of 15.2 m in peak spikes were 210-300 kW/m2 (NOTE: about 35
kW/m2 - 1% fatality in 10 seconds).

Source: Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th Seminar on Fire and Explosion Hazard, Edinburgh, UK, 23-27 April 2007, pp. 2154-2161.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Projectiles

• Type IV (stand-alone): the largest tank projectile fragment

was the 14 kg top half of the tank found 82 m away from
the original tank location.
• Type III (SUV test): a large tank fragment found 41 m
from the SUV. Fragment projectiles from the SUV were
found at distances up to 107 m. It is possible that
undiscovered fragments may have travelled even further.
• A car could act as a “missile” (22 m displacement!)
• EU Regulations 2010: “Hydrogen components …must not
project beyond the outline of the vehicle”.
Source: Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th Seminar on
Fire and Explosion Hazard, Edinburgh, UK, 23-27 April 2007, pp. 2154-2161.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Fire resistance of storage vessels

➢ Current level of fire resistance rating (FRR) for

hydrogen storage tanks remains low: it ranges from
3.5 to 12 minutes (recent research at UU
demonstrated FRR more than 1 hr 50 mins).
➢ Due to the relatively large orifice diameter (4-6 mm)
of a TPRD the length of a flame produced is too
high (from 10 to 15 m) and a hazard distance is
around 50 m.
➢ Unacceptable for life safety and property
protection!
Fire test, CNG tank not equipped with a PRD

European regulations require that on-board storage passes a bonfire test. However, there is no requirements to
FRR of a tank to inform the public and firemen.
European Hydrogen Train the Trainer Programme for Responders
 Hydrogen storage
Fire protection of hydrogen storage tanks

• A composite tank coated with a • A composite tank wrapped with a ceramic blanket
sprayed ceramic insulating material (Gambone and Wong, 2007). Intact after having been
(Gambone and Wong, 2007). exposed to an intense localized fire for 45 minutes.
Source: Gambone, L.R. and Wong, J.Y., Fire Protection Strategy for Compressed Hydrogen-Powered Vehicles, ICHS2, 2007).

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Fire protection of hydrogen storage tanks

Concept of thermal insulation

• Protective encapsulation not only
imparts fire resistance but also
provides an additional level of impact
protection (Gambone and Wong,
2007).
• This may allow tank designers to
reduce the amount of reinforcing
composite material which could reduce
the cost and weight of storage systems.

Source: Gambone, L.R. and Wong, J.Y., Fire Protection Strategy for Compressed Hydrogen-Powered Vehicles, ICHS2, 2007).

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Safety strategies for inherently safer design

• With one layer of intumescent paint applied to Type IV tank an

increase of the FRR by an order of magnitude!
• There is an urgent need to demonstrate increased fire resistance of
Type III and IV tanks used by car manufacturers (if OEMs say there
is “no safety problems” – they have to demonstrate actual fire
resistance rating of their on-board storage to the general public –
“to pass” bonfire test is not enough!)

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Intumescence

• Intumescence is a versatile method for providing

reaction and resistance to fire to materials

• When heating beyond a critical temperature, the

intumescent material begins to swell and then
Intumescent coating before the fire exposure to expand forming an insulative coating limiting
heat and mass transfer

• A multi component system- essentially consists

of a char former (e.g. pentaerythritol); acidic
component (e.g. ammonium polyphosphate);
a spumific/blowing agent (e.g. melamine)
Intumescent coating after the fire exposure

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
TPRDs with plane nozzles

Round jet

Plane jet

Plane jet

Reduced size of flammable envelope; reduced jet fire length; faster hydrogen concentration decay
Source: Makarov, D, and Molkov, V. (2013). Plane hydrogen jets. International Journal of Hydrogen Energy, Vol. 38, no. 19, pp. 8068–8083.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Storage tank with three fire resistant layers

Fire resistance: 1-2 hour (instead of 5 min)

Flame length: less than 1 m (instead of 15 m)
Automated control of tank aging

Current

Novel
Work-in-progress at Ulster

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Potential hazards of on-board GH2 storage (1/4)

• Difficulty in identification of hydrogen release: it is odourless, colourless and

tasteless gas. Odorants cannot be used.
• Hydrogen can cause embrittlement of metals, leading to cracks
formation/propagation and hydrogen leak. This may result in the decrease of a
material’s strength and consequently in the container’s fracture.
• Accumulation of hydrogen over time in enclosures such as a garage or
mechanical workshop, a vehicle passenger compartment. Asphyxiation might
occur due to displacement of air with hydrogen.
• Formation of hydrogen-oxygen or hydrogen-air flammable mixtures. The intake
of flammable mixture into a building ventilation system may lead to deflagration or
even to detonation.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Potential hazards of on-board GH2 storage (2/4)

• High pressure hydrogen jets may cut bare skin (Hammer,

1989).
• Overpressure and impulse (eardrum damage, tank rupture,
flying debris, shattered glass etc).
• Pressure peaking phenomenon (a garage collapse in 1
sec).
• Hydrogen ignites easily (minimum ignition energy for
hydrogen combustion is 0.017 mJ, which is 10 times lower
compared to other fuels). A static spark can ignite hydrogen.
• Hydrogen flames are invisible in the daylight.
Source: Hammer, W (1989). Occupational Safety Management and Engineering, 4th edition, Prentice Hall, Englewood Cliffs, New Jersey, 1989, ISBN 0-
13-629379-4, chapter 19.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Potential hazards of on-board GH2 storage (3/4)
Before the fire
• Hydrogen burns rapidly and does not produce smoke.
Flash fire, jet fire.
• An external fire, heat or thermal radiation can cause a
mechanical rupture of a tank. Fire resistance up to 12
minutes (publicly available) before catastrophic
failure.
After the fire test
• In case of TPRD malfunction a worst-case scenario: a
rupture (catastrophic failure) of hydrogen storage
tank, producing fireball, blast waves and burning
projectiles.

Source: Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th
Seminar on Fire and Explosion Hazard, Edinburgh, UK, 23-27 April 2007, pp. 2154-2161.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Potential hazards of on-board GH2 storage (4/4)

Video: CNG tank bonfire, no TPRD

https://www.youtube.com/watch?v=dzeqGxI
ssk8&list=PLlphoM9ggM3Rf-
Npmdq0S3WrCSpx0U4SL&index=8

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Liquefied hydrogen (LH2) storage (1/2)

• Tanks for LH2 can store more hydrogen compared to those for GH2: volumetric capacity of LH2
0.070 kg/L as opposed to 0.030 kg/L for GH2 tanks at 70 MPa.
• LH2 stored at low (cryogenic) temperatures -253 oC and near-ambient pressure (0.6 MPa).
• Sufficient level of tanks insulation needed to prevent the release of evaporated gas.
• Major industrial gas suppliers have cryogenic tanker delivery lorries.
• Hydrogen refuelling stations and airspace applications (higher energy density than GH2).
Issues:
• Boil-off phenomenon (rate of 0.3-3% per day).
• High level of energy required for liquefaction (about 30% of heating value of hydrogen)
• Volume, weight and costs of tanks

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Liquefied hydrogen (LH2) storage (2/2)

Double-walled vacuum insulated vessel (light-weight steel alloys)

Components of LH2
storage:
• LH2 storage
container
• Shut-off devices
• A boil-off system
• TPRDs
• The interconnecting
piping (if any) and
fittings between the
above components

Source: GTR, Proposal for a global technical regulation (gtr) on hydrogen fuelled vehicles, 2013.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Safety issues of LH2 storage (1/2)

• Loss of containment: damage of the external tank walls can lead to the
disruption of vacuum, causing heating and subsequent pressure rise inside the
vessel.
• Condensed air may form an oxygen enriched atmospheres in the vicinity of LH2
storage (risk of explosion if external wall tank is damaged)
• Boil-off losses: concerns when vehicles parked for a long time (pressure builds
up until boil-off valves open.
• Ice formation: low temperatures may result in ice build-up on storage elements
(e.g. valves, dewars) leading to an excessive exterior pressures, and to possible
rupture of the vessel.
European Hydrogen Train the Trainer Programme for Responders
 Hydrogen storage
Safety issues of LH2 storage (2/2)

• Boil-off/evaporation can be caused by:

• Ortho-para H2 conversion: conversion of ortho- to para-hydrogen is an exothermic reaction. If the
unconverted normal hydrogen is placed in a storage vessel, the heat of conversion will be released
within the container, which leads to the evaporation of the liquid.
• Residual thermal leaks: the heat leakage losses are proportional to the ratio of surface area to the
volume of the storage vessel. The shape of cryogenic vessel should be spherical since it has the least
surface to volume ratio. A big cause of heat leaks in cryogenic storage is through the support struts in
the vessel.
• Sloshing: a motion of LH2 in a vessel due to acceleration or deceleration, which occurs during its
transportation by tankers . Some of the impact energy of the liquid against the vessel is converted to
thermal energy.
• Flashing: occurs when LH2 at a high pressure is transferred from trucks and rail cars to a low pressure
vessel

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
LH2 releases (1/2)

• In case of a LH2 leak or spill, a hydrogen cloud will be

formed; could flows horizontally for some distance or even
downward, depending on the terrain and weather condition.
• Volume ratio of LH2 to GH2: 848
Solid deposit formation, HSL experiment, UK [1]
• Solid deposits (in HSL experiments) formed by condensed
air and LH2. May be enriched with oxygen (possible
explosion-in HSL large scale experiments one secondary
explosion occurred).
• Ignition of LH2 vapour cloud: ignitions occurred in 10 of the
14 tests undertaken by HSL.

Sources:
LH vapour cloud ignition, HSL experiment, UK [2]
2
[1] Royle M, Willougby D, 2012. Releases of unignited liquid hydrogen, Buxton: Health and Safety Laboratory. [2] Hall J, Willoughby DB, Hooker P, 2013. Ignited Releases of Liquid Hydrogen, Buxton: Health and Safety Laboratory.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
LH2 releases (2/2)

Videos of LH2 spill outdoor

https://www.youtube.com/watch?v=pD_OrWVJaW4&list
=PLlphoM9ggM3Rf-Npmdq0S3WrCSpx0U4SL&index=11

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Cryo-compressed hydrogen storage

• Combines storage of hydrogen at cryogenic temperatures in a vessel that

can be pressurised (e.g. to 35 MPa)
• Developed by Lawrence Livermore National Laboratory (LLNL) and BMW
Group.
• Liquid hydrogen or cold compressed hydrogen can be stored.
Advantages:
• higher hydrogen density compared to LH2 and GH2 storage options
• potential improvement in weight, volume and overall costs of tanks
• radically lower theoretical burst energy of cryogenic hydrogen.
Source: Argonne National Laboratory Report , 2009 (ANL/09-33)

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Leak-no-burst safety technology

Ulster’s IP:
International (PCT)
Application No
PCT/EP2018/053384

• Two composites with different thermal properties. External composite “TPL” has lower thermal conductivity, the
internal part of wall composite “FRP” has higher thermal conductivity.
• Once the liner is melted, hydrogen starts to leak through tank wall safely as insignificant leak and the internal
pressure reduces before the composite wall loses its load-bearing ability.
European Hydrogen Train the Trainer Programme for Responders
 Hydrogen storage
Novel storage techniques

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Reference (1/3)
1. DoE. Hydrogen storage (2015). Available from: http://energy.gov/eere/fuelcells/hydrogen-storage [accessed on 06.11.20].
2. NASA. Summary: space applications of hydrogen and fuel cells. Available from: http://www.nasa.gov/topics/technology/hydrogen/hydrogen_2009.html [accessed on 06.11.20].
3. Introduction to Hydrogen for Code Officials, U.S. Department of Energy, Washington DC. Available from: http://www.hydrogen.energy.gov/training/code_official_training/ [accessed on
06.11.20].
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6. Zuettel, A (2013). Hydrogen: production, storage, applications and safety. H2FC European Technical School on Hydrogen and Fuel Cells. 23-27 September 2013, Crete, Greece.
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Inland Transport Committee. World Forum for Harmonization of Vehicle Regulations, 160th Session, Geneva, 25-28 June 2013.
9. Mafeld, A. (2015). CPVs: Regional trends in the global market. JEC Asia: Composite Pressure Vessels Forum. Singapore, October 22, 2015.
10. Barthelemy, H (2009). Hydrogen storage technologies: compatibility of materials with hydrogen. Teaching materials of the 4th ISCARW, Corsica, June, 2009.
11. Klebanoff, L (Ed) (2012). Hydrogen storage technology: Materials and applications. Boca Raton: CRC Press. Taylor&Francis.
12. Warner, MJ (2005) Low cost, high efficiency, high pressure hydrogen storage tanks, Quantum Technologies, Irvine, CA. Available from:
https://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/04_warner_quantum.pdf [accessed on 06.11.20].
13. EU No 406/2010, Commission Regulation of 26 April 2010 implementing Regulation (EC) No 79/2009 of the European Parliament and of the Council on type-approval of hydrogen-
powered motor vehicles. Official Journal of the European Union. Vol. 53, 18 May 2010. Available from: http://eur-
lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2010:122:FULL:EN:PDF [accessed on 06.11.20].
14. Sunderland, P (2010a). Hydrogen vehicles and safety regulations in the U.S. Teaching materials of the 8th ISCARW, Belfast, UK, June 2010.
15. Malek, MA (2006). Pressure relief devices ASME and API code simplified. New York: McGraw Hill.
16. Motor Vehicle Fire Investigation, computer-based training accessed. Available from: http://depts.washington.edu/vehfire/topics.html [accessed on 06.11.20].
17. GTR, Proposal for a Global Technical Regulation (GTR) on hydrogen fuelled vehicles, 2013. ECE/TRANS/WP.29/GRSP/2013/41. United Nations. Economic Commission for Europe.
Inland Transport Committee. World Forum for Harmonization of Vehicle Regulations, 160th Session, Geneva, 25-28 June 2013.

European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Reference (2/3)

18. Royle, M and Willoughby, D (2012). Releases of unignited liquid hydrogen. HSL Report XS/11/70. Available from HSL: Buxton.
19. Hall J, Willoughby DB, Hooker P, 2013. Ignited Releases of Liquid Hydrogen, Buxton: Health and Safety Laboratory
20. Mays, T. (2014). Scientific progress and technological bottlenecks in hydrogen storageH2FC European Technical School on Hydrogen and Fuel Cells. 23-27 June 2014, Crete,
Greece.
21. Zalosh, R (2007). Blast waves and fireballs generated by hydrogen fuel tank rupture during fire exposure. Proceedings on the 5th Seminar on Fire and Explosion Hazard, Edinburgh,
UK, 23-27 April 2007, pp. 2154-2161.
22. Weyandt, N (2006). Vehicle bonfire to induce catastrophic failure of a 5000-psig hydrogen cylinder installed on a typical SUV, Motor Vehicle Fire Research Institute. Report.
December, 2006. Available from: www.mvfri.org [accessed 06.11.20].
23. Barry, TF (2003). Fire exposure profile modelling: some threshold damage limit (TDL) data. A whitepaper by TFBarry Publications, September 2003.
24. Molkov, V and Kashkarov, S (2015). Blast wave from a high-pressure gas tank rupture in a fire: stand-alone and under-vehicle hydrogen tanks. vol. 40, no. 36, pp. 12581–12603,
2015.
25. Molkov, V (2012). Fundamentals of hydrogen safety engineering, Part I and Part II. Available from: www.bookboon.com, free download e-book.
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applications. International Journal of Hydrogen Energy, Vol. 37, pp. 17630-17638.
27. Gambone, LR and Wong, JY (2007). Fire protection strategy for compressed hydrogen-powered vehicles. 2nd International Conference on Hydrogen Safety, San Sebastian, Spain,
11-13 September, 2007.
28. Webster, C (2010). Localized Fire Protection Assessment for Vehicle Compressed Hydrogen Containers. Report DOT HS 811 303.
29. Makarov, D, and Molkov, V. (2013). Plane hydrogen jets. International Journal of Hydrogen Energy, Vol. 38, no. 19, pp. 8068–8083.
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32. UN WP.29/GRSP/GTR 13-2: https://wiki.unece.org/download/attachments/87622122/GTR13-7-
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European Hydrogen Train the Trainer Programme for Responders

 Hydrogen storage
Reference (3/3)

33. Mair, G. W.: Presentation at UN WP.29/GRSP/GTR 13-2-07: https://wiki.unece.org/download/attachments/87622122/ GTR13-715_BAM_Safety-minimum_burst_ratio%202019-11-

07rev.pdf?api¼v2. [accessed on 17.11.20].

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35. Molkov V., Makarov D., Kashkarov S. Composite vessel for hydrogen storage, European Patent Application No 18706224.5, 2019.

36. Regulation No. 134. Uniform provisions concerning the approval of motor vehicles and their components with regard to the safety-related performance of hydrogen fuelled vehicles
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38. M. Dadashzadeh, S. Kashkarov, D. Makarov, and V. Molkov, “Socio-Economic Analysis and Quantitative Risk Assessment Methodology for Safety Design of Onboard Storage
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39. N. Weyandt, “Analysis of Induced Catastrophic Failure Of A 5000 psig Type IV Hydrogen Cylinder,” Southwest Research Institute report for the Motor Vehicle Fire Research Institute,
01.06939.01.001, 2005.

40. N. Weyandt, “Vehicle bonfire to induce catastrophic failure of a 5,000-psig hydrogen cylinder installed on a typical SUV,” Southwest Research Institute report for the Motor Vehicle
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Syst. 7(3):1027-1035, 2014.

European Hydrogen Train the Trainer Programme for Responders

This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking (JU) under grant agreement No
875089. The JU receives support from the European Union’s Horizon 2020 research and innovation programme and
United Kingdom, France, Austria, Belgium, Spain, Germany, Italy, Czechia, Switzerland, Norway

European Hydrogen Train the Trainer Programme for Responders