H2 Technology Training Course

Session 8: Risk and Safety

24th August 2023
 In this session, we will review

• Gas and Flame Detection

• Risks including fire and explosion
Fire and Explosion Risks
 Causes of hydrogen safety accidents and caused by
equipment failures

Gas leakage from parts such as pipeline valves and fittings is the main cause of
hydrogen accidents. Most of the times due to material integrity issues.
Flow chart of hazard occurrence due to hydrogen
leakage
 Fire Risks

• Wide flammability range (4- 74% in air) and low ignition

energy (0.02 mJ)
• For a hydrogen fire to occur, an adequate concentration of
hydrogen, the presence of an ignition source and the right
amount of oxidizer (like oxygen) must be present at the
same time.

• Potential for spontaneous ignition (relatively higher

ignition probability than HC releases)
• Flame is almost invisible with low radiant heat due to the
absence of carbon and the presence of heat absorbing
water vapor created when hydrogen burns.
 Dispersion

• Hydrogen fires are different to fires involving other fuels. When heavier fuels and
hydrocarbons leak, they pool close to the ground. When hydrogen leaks, it rapidly
disperses upwards. The ignition is less likely, but it ignites and burns more easily and
quicker than petrol or diesel.
 Explosion Risks

• An explosion cannot occur in a tank or any contained location that contains

only hydrogen. An oxidizer, such as oxygen must be present in a concentration
of at least 10% pure oxygen or 41% air.
• Hydrogen can be explosive at concentrations of 18.3- 59% and although the
range is wide, it is important to remember that gasoline can present a more
dangerous potential than hydrogen since the potential for explosion occurs
with gasoline at much lower concentrations, 1.1- 3.3%.
• Little likelihood that hydrogen will explode in open air, due to its tendency to
rise quickly.
• Even a spark of static electricity is enough to set off an explosion when
hydrogen is available.
Typical fireball propagation of hydrogen tank
explosion in time sequence
Types of hydrogen self-ignition
Recent hydrogen accidents with explosion and fire
Gas and Flame Detection
 Gas Detection Technologies

• Gas detection represents the first line of defense in the case of a hydrogen release.
Ideally, actions can be taken to stop the hydrogen leak before a flame or explosion.
• Odorization of hydrogen gas with a compatible odorization agent should be considered
to also aid detection of a hydrogen leak.
 Leak detection system requirements

• High sensitivity
• Fast response
• Wide dynamic range
• Superior selectivity and resistance to typical interferences (such with the
presence of other gases and humidity)
• The sensor must be very stable
• Long lifespan and tolerable false positive response rates
• Operation near room temperatures
Leak detection technologies
 Gas Detection Technologies

• An infrared gas detector responds to gases that absorb IR radiation – such as methane
and propane (hydrocarbons). But hydrogen cannot absorb IR radiation, so IR gas
detectors will not detect it and should not be used.
• Catalytic bead type detectors are suitable for industry applications. They can detect
hydrogen at lower flammable limit (LFL) levels (~4% by volume).
• A catalytic bead sensor detects any combustible gas that combines with oxygen to
make heat. If the gas can burn in air, this detector will sense it.
• Sensors need to be located close to and above the location where the leak is likely to
occur
 Gas Detection Technologies:
Catalytic Bead Detectors

• The catalytic bead sensor is a type of sensor that is used for combustible
gas detection. It has been used for ~50 years.

• The catalytic gas sensor usually consists of a matched pair of platinum wire
wound resistors, one of which is encased by a bead of ceramic.

• This matched pair is then enclosed behind a flameproof sinter, or porous

filter.

• The catalytic bead has a catalyst coated onto the bead surfaces and causes
combustible gas to burn at lower concentrations and temperatures than an
untreated bead in air.

• The reference bead, or compensator is not coated with a catalyst. Gas

encountering it will not burn until it reaches the lower explosive limit (LEL).

• When combustible gas contacts the catalyst bead, heat is released as result
of the gas - bead interaction. The energy produced causes a change in
resistance from the catalytic bead, while the reference bead maintains a
steady resistance. The variation in resistance is measured by the
Wheatstone bridge and indicates the presence of combustible gas.
 Gas Detection Technologies:
Catalytic Bead Detectors (Continued)

• The catalytic bead sensors performance is impacted by:

• Poisoning Contaminant compounds, such as lead, silicones, phosphate, and sulfur-based substances
can decompose on the catalyst, forming a solid coating on its surface which decreases the
sensitivity of the sensor leading to failure.

• Temporary Inhibition Contaminant compounds, such as volatile organic compounds (VOCs) and hydrogen
sulfide (H2S), can be absorbed by the catalytic bead catalyst which creates a blockage in
the reaction sites.

• Sensor Overload When the sensor is exposed to high concentrations of combustible gas the sensor
can lose sensitivity

• Low Oxygen Because catalytic bead sensors work by burning combustible gas, they rely on adequate
oxygen levels to provide accurate readings of gas levels.

• Mechanical Breakage The sensors use fine platinum wires embedded in the bead as the source of heat.
Mechanical stress, along with the heat of the beads, and exposure to industrial chemicals,
can weaken the contact between the wire and the bead surface, leading to failure.
 Flame Detection

• A hydrogen flame poses special dangers because human senses cannot

detect it. The flame emits very little radiant heat, and there is little warning that
it is there.
• The safest protection strategy against a hydrogen flame is to prevent
hydrogen gas from escaping, however if it does escape a gas detection
system should be in place to alert operators before it ignites.
• If the leak does ignite, the flame needs to be detected quickly and accurately.
 Flame Detection Technologies

• Hydrogen burns a very pale blue to nearly

invisible flame
• Previously, the broomstick method was
used where a dry grass broom was held
in front of the operator while sweeping
the air. If the broom caught fire it meant
that a hydrogen flame was ahead.
• Fortunately, safety system manufacturers
offer tools beyond the broom. They’ve
developed technologies such as:
• Thermal Detectors
• UV Flame Detectors
• Multispectrum IR Flame detectors.
 Flame Detection Technologies: Thermal Detectors

• Detectors of this type will not alarm until the temperature of the area being
monitored exceeds the detector’s trip point, so it is logical to position them
directly above the possible site of a hydrogen flame.
• However, the source of a hydrogen leak may create a flame that is directed
away from the detector.
• The hydrogen flame’s low IR radiation may not be enough to set the radiant
heat detector into alarm. Thermal detectors are helpful, but proper
positioning is the biggest challenge.
 Flame Detection Technologies: UV Detectors

• UV detectors use basic anode/cathode vacuum tubes to sense UV radiation

emitted by a flame.

• UV radiation enters the vacuum tube through a quartz window and strikes the
cathode.

• The energy from the UV photon releases a photo electron and creates an
electrical impulse as it travels to the anode. This is a basic technology that
dates back to the beginning of the 20th century.

• Hydrogen flames, compared to hydrocarbon flames, emit little visible light and
little IR radiant heat. Instead, energy is radiated primarily in the UV band.
Therefore, UV detectors excel at detecting hydrogen flames.

• UV detectors have a good detection range and can see a 24-inch plume flame
up to 50 feet away.

• A drawback of UV detectors is that they are sensitive to arcs, sparks, welding,

lightning, and other UV-rich sources. When those relatively safe conditions are
present, UV detectors could go into alarm condition. False alarms can be
expensive and can reduce people’s sensitivity to potential hazards. UV
detectors, with their very fast response time and good detection range, are
best suited for applications where the false-alarm sources can be controlled.
 Flame Detection Technologies: Multispectrum IR
Detectors
• Multispectrum IR flame detectors use a combination of IR sensor filters
and software analysis to both see the flames and reduce false alarms.
Some multispectrum IR detectors have been designed specifically to
detect the low-level IR radiation of hydrogen flames using a unique set of
IR filters.

• These special multispectrum IR flame detectors have very good detection

range with good response time to the low levels of IR from hydrogen
flames, but do not incur false alarms for arcs, sparks, welding, and
lightning.

• The multispectrum IR detector has complete solar resistance and is

insensitive to artificial lights and most “blackbody” radiation, which plague
other detection technologies.

• By selecting the optimum IR filter set, some available detectors have

doubled the UV range and can detect a 24-inch plume flame at 100 feet.
The result is increased flame sensitivity with discrimination of non-flame
sources in situations where traditional flame detectors are unsuitable.

• Their detection range is reduced with the presence of water or ice on the
lens. To mitigate the problem, some detectors are manufactured with lens
heaters that melt ice and accelerate the evaporation of water.
Hydrogen fire
 Other Safety Concerns: Risks of LH2-Liquid air

• Liquid hydrogen can form below -240°C

• Oxygen becomes a liquid below -190°C
• Exposed cryogenic hydrogen piping can
cause liquid oxygen to condense and form
pools on surface
• Everything is a fuel when liquid oxygen
is present
• Insulation must be applied to ensure
no surface exposed to air in the
cryogenic hydrogen facility is less
Prevention of liquid air formation is
than -150°C paramount for hydrogen piping systems
 Other Safety Concerns: Risks of LH2-Frostbite

• If liquid hydrogen should escape from its tank and contact skin it can
cause severe frostbite or even loss of extremities. However, to keep
hydrogen ultra-cold today, liquid hydrogen containers are double-walled,
vacuum-jacketed, super-insulated containers that are designed to vent
hydrogen safely in gaseous form if a breach of either the outer or inner
wall is detected, reducing the likelihood for human contact.
Other Safety
 Design Safety in H2 and NH3 production
• 19th Jul 2019 massive explosion and fire at the Henan Gas plant in Yima city, China

• 30+ fatalities, major injuries and damage to property within 3km of the facility

• The root cause lay within the Air Separation Unit (ASU)

• This incident is not common but is not isolated:

• 8 explosions on Chinese ASUs since 1973

• 6th Aug 2007 explosion at NIGC ‘s ASU in Al-Jubail, Saudi Arabia (feeding SABIC Ethylene Oxide facility)

• 25th Dec 1998 explosion at an ASU at Shell’s MDS plant in Bintulu, Malaysia

• Why do ASUs explode?

• Most feared reason is accumulation of hydrocarbons in liquid oxygen in the main condenser unit

• Intake of hydrocarbons with the air is inevitable. Extremely low concentrations of methane, acetylene and other
light hydrocarbons are present in the air from natural causes or due to emissions from neighbouring
petrochemical processing operations

• Hydrocarbons at low concentrations in air no risk (outside flammable range). Risk of hydrocarbons accumulate with
the liquid oxygen
 Mitigations
• Use of latest standards for design/fabrication of hydrogen facilities eg: ASME B31.12 & ISO standards

• Prevent entirely the risk by avoiding pure oxygen in hydrogen and ammonia production

• If ASU unavoidable: pre-purification of the air; maintaining the condenser unit in a fully submerged condition; use of
adsorbers in the liquid oxygen phase to remove hydrocarbons and purging liquid oxygen from the main condenser to
prevent accumulation
 Further reading and study material

• Wang et al., 2023, Minireview on the Leakage Ignition and Flame Propagation
Characteristics of Hydrogen: Advances and Perspectives, Energy Fuels, 37, 8,
5653-5666
• Yang et al., 2021, Review on hydrogen safety issues: Incident statistics, hydrogen
diffusion, and detonation process, International Journal of Hydrogen Energy, 46,
61, 31467-31488.
• Abohamzeh et al., 2021, Review of hydrogen safety during storage, transmission,
and applications processes, Journal of Loss Prevention in the Process Industries,
72, 104569.
• Wang et al., 2023, Explosion of high pressure hydrogen tank in fire: Mechanism,
criterion, and consequence assessment, Journal of Energy Storage, 72, C, 108455.
 Further reading and study material

• Hübert et al., 2011, Hydrogen sensors – A review, Sensors and Actuators B:

Chemical, 157, 2, 329-352