FIRE SAFETY FOR HYDROGEN

Written BY: Ir. Tan Yoke Lee (MIEM, Mi-FIRE E)

yokeleetan71@gmail.com
Reference: Wikipedia, Ignition sources and Prevention PPT by HY
Responders, Fire Protection and Suppresion by Hydrogen Tools
website
FIRE SAFETY FOR HYDROGEN

Fire is a chemical chain reaction which takes place with the

evolution of heat and light.

In order for a fire to take place there are 3 main ingredients that
must be present: Oxygen, Heat and Fuel.

Combustion is a high-temperature exothermic (heat releasing)

redox (oxygen adding) chemical reaction between a fuel and an
oxidant, usually atmospheric oxygen, that produces oxidized,
often gaseous products, in a mixture termed as smoke.
FIRE SAFETY FOR HYDROGEN

Fire requires the complete four components to happen.

The four components are:-
1. Fuel source
2. Ignition source which produces the heat to ignite the
fuel source. Example cigarette butts can be ignition
source but seldom the fuel itself.
3. Oxygen is the air surrounding the fuel when burning.
4. Chemical reaction is what enables the combustion
process to propagate and continue. Without chemical
reaction, you cannot have fire.
In order to stop the combustion process, the control
measures can be in the way of eliminating any of the above
four components.
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Understanding fuel
• In order for fuel to be flammable, the mixture of fuel in air must be within lower and upper explosive
limit, ie LEL and UEL. When fuel is below LEL, there is simply not enough fuel present in vapour form to
burn. When fuel is higher than UEL, the fuel is too rich to burn.

The term explosive limit and flammability

limit is used interchangeably.
 FIRE SAFETY FOR HYDROGEN

Flash point is the temperature at which the fuel will

produce sufficient vapour (at lower flammability limit)
to combust with the PRESENCE OF COMPATIBLE
IGNITION SOURCE.

At temperature above Tu and below autoignition

region, the fuel will not burn as the fuel will be too rich.

Autoignition temperature is the temperature at which if

the fuel is heated to, will burn by itself without the help
of any ignition source. If fuel is heated up to this
temperature, the combustion could be explosive
depending on the amount of fuel available. Auto
Tu ignition temperature of hydrogen is about 510 deg C
but in presence of Pt catalyst can be lowered down to
70 deg C.
 FIRE SAFETY FOR HYDROGEN

Fire Chemistry and Ignition Source

Example of hydrocarbon combustion (ie gasoline fuel),

2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(g) + energy
This reaction refers to complete combustion where oxygen
is not limited. Where it is limited, we may get byproducts
such as carbon monoxide, smoke, etc.

Example of hydrogen combustion

2H2(g) + O2(g) → 2H2O(g) + energy
The flame is almost colourless. Mixtures of hydrogen and
oxygen (or hydrogen and air) can be explosive when the
two gases are present in a particular ratio, so hydrogen
must be handled very carefully. In atmospheric air rather
than pure oxygen, hydrogen combustion may yield a small
amount of nitrogen oxides with the water vapor.

Extra care is required when dealing with hydrogen fire as it

is almost colourless.
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Fire Chemistry and Ignition Source

In order for the above combustion process to start, we need

to overcome the activation energy of reaction which is
also known as minimum ignition energy. In terms of
cars, it is the sparks produced by the spark plug. Thus
MIE is an energy that needs to be introduced to start
the chemical reaction.

Energy released or absorbed is the difference in energy

between the reactants and products.
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Fire Chemistry and Ignition Source

As can be seen, the MIE for hydrogen is only 0.011mJ as

compared to gasoline which is 0.80mJ and propane of 0.25mJ.

Many ignition sources can produce sufficient energy to start a

hydrogen fire. For eg. A weak spark caused by static electricity
discharging from a human body may be sufficient to ignite the
hydrogen/ air mixture.

It is to note that many ignition sources have ignition energy

higher than 10mJ, thus practically all fuels would be ignited if
their fuel/ air ratio exceeds the LFL
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Fire Chemistry and Ignition Source

MIE of hydrogen as compared to other fuels

 FIRE SAFETY FOR HYDROGEN

Fire Chemistry and Ignition Source Thus a source with ignition energy of 0.24mJ will not
ignition methane or propane but will ignition hydrogen
mixture with air within the concentration of 6.4% to
58%.

A source with energy of 1mJ will ignite hydrogen with

air within the concentration of 6% to 64%.
0.24
Note that less energy would be required to ignite a
mixture that is closer to its stoichiometric composition.
The stoichiometric concentration would be the dip of
the MIE curve.
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Typical Ignition Sources Electrical

Electrical sources:

•Electric sparks (e.g. from electrical equipment)

•Static discharges (e.g. in ungrounded particulate filters)
•Electric arc (switches, electric motors, portable phones, pagers and radios).
•Lightning discharge (e.g. lightning strikes near the vent stack)
•Electrical charge generated by equipment operation (compressors, generators, vehicles and other construction
equipment)
•Electrical short circuits or other electrical equipment
•Electrified particulates
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Typical Ignition Sources Mechanical and Thermal

Mechanical sources:
• Mechanical sparks (from rapidly closing valves)
• Mechanical impact and/or friction, for eg impact of heavy objects falling on the floor.
• Metal fracture
• Mechanical vibration and repeated flexing

Thermal sources:
• Hot surfaces (e.g. heating equipment)
• Open flames
• Hot jets
• Exhausts (e.g. combustion engines and exhaust stacks)
• Explosive charges (e.g. charges used in construction, fireworks or pyrotechnic devices)
• Catalysts, explosives and reactive chemical materials
• Shock waves and/or fragments can be caused by accidental release of hydrogen at high pressure.
• Reflected or repeated acoustic and shock waves
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Typical Ignition Sources Others

Other sources:

•Ionizing radiation (radioactivity)

•Electromagnetic radiation
•Ultrasonic radiation
•Light (laser/flash)
•Adiabatic compression (pressure increase) . Thus it is important to consider the condition of hydrogen
undergoing process of pressurisation.
 FIRE SAFETY FOR HYDROGEN

Static Electricity

Why is static electricity discharge dangerous?

• Most people are just familiar with static electricity discharge from lightning strike.
• It is however a phenomena that we cannot see but it may be present anywhere.
• Any movement of insulating gas and liquid could cause static electricity to form like filling of tanks, etc. Even the
release of hydrogen from blow down unit in a process plant can actually charge up the hydrogen; hydrogen being
an insulator in both gaseous and liquid state. Hydrogen is released in high velocity and high pressure and can build
up static charges as the high velocity hydrogen moves across air in the blow down phase.
• Static electricity build up tend to be more prominent when the humidity is low. The dry air prevents continuous
discharge of charges which eventually build up and when the level is quite high, it can discharge as static electricity
discharge.
• Prevention of static electricity build up tends to be more focused in the electronic industry as any high voltage
discharge can destroy the electronic component.
• However, in presence of fuel within LEL and UEL, static electricity can be a competent dangerous source of
ignition. It is something that is difficult to monitor as the build up charges can be anywhere, thus you cannot install
something like a gas detector to monitor.
 FIRE SAFETY FOR HYDROGEN
Static Electricity
Types of electrostatic discharges

Spark discharge is a single plasma channel between the high potential conductor and an earthed conductor.
• The energy from a spark discharge from an isolated conductor is calculated as E=CV2/2,
• where C is the capacitance of the item (Farad), and V is the potential (voltage).
Brush discharge is a discharge between a charged insulator and a conducting earthed point.
• It is characterised by many separate plasma channels, combining at the conductor. As the charged surface is a non-
conductor, a capacitance and hence energy cannot be determined.
• The discharge energy can be 10-20mJ.
Corona discharge is a silent, usually continuous discharge which is characterised by a current but no plasma channel.
• A corona discharge is an electrical discharge caused by the ionization of a fluid such as air surrounding
a conductor carrying a high voltage. It represents a local region where the air (or other fluid) has
undergone electrical breakdown and become conductive, allowing charge to continuously leak off the conductor
into the air. A corona discharge occurs at locations where the strength of the electric field (potential gradient)
around a conductor exceeds the dielectric strength of the air. It is often seen as a bluish glow in the air adjacent to
pointed metal conductors carrying high voltages, and emits light by the same mechanism as a gas discharge lamp.
• A corona discharge is able to ignite a hydrogen–air mixture without there being a discrete spark or single discharge
event.
• The discharge energy is smaller than brush and spark discharge and is in the order of magnitude of 0.1mJ.
Therefore, brush discharges are considered an explosion hazard, while corona discharges are not.
 FIRE SAFETY FOR HYDROGEN
Static Electricity
Types of electrostatic discharges

Spark discharge calculation for typical hydrocarbon.

• MIE for typical hydrocarbon is about 0.29mJ
• Capacitance of a normal healthy human being is about 100pF.
• Using equation

Where E=energy, C= capacitance, the critical voltage to cause sufficient discharge of energy that is greater than MIE=
Sqrt ((2 x 0.29 x 10-3)/(100 x 10-12 )) = 2.4kV
• Di electric strength of air is 30kV/cm.
• Thus minimum gap to prevent discharge @2.4kV = 2.4/30 cm = 0.8mm between the conductor and earthed point. The
quenching gap applied in industry = 2-3mm which corresponds to 6kV to 9kV discharge.
 FIRE SAFETY FOR HYDROGEN
Static Electricity
Types of electrostatic discharges

Spark discharge calculation for hydrogen in air mixture

• MIE for typical is about 0.017mJ
• Capacitance of a normal healthy human being is about 100pF.
• Using equation

Where E=energy, C= capacitance, the critical voltage to cause sufficient discharge of energy that is greater than MIE=
Sqrt ((2 x 0.017 x 10-3)/(100 x 10-12 )) = 583V
• Di electric strength of air is 30kV/cm.
• Thus minimum gap to prevent discharge @0.583kV = 0.583/30 cm = 0.2mm between the conductor and earthed point.
The quenching gap applied in industry = 0.64mm which corresponds to discharge voltage of 1.9kV .

Thus, electrostatic charging of people who refuel their vehicles with petrol rarely gives rise to ignitions. It
is significant that the voltage required for hydrogen to be ignited is below 2 kV. This voltage can be
generated easily on people, without them being aware of it, standing on an insulating surface, so there is a
potential for personnel to ignite hydrogen leaks very easily, without any apparent ignition source being
present (Astbury and Hawksworth, 2007).
 FIRE SAFETY FOR HYDROGEN

Sudden release of hydrogen in high pressure pipe or container

The mechanism:
• The disk separates high pressure hydrogen from the air in a pipe (both gases are at ambient temperature).
• After the disk rupture a shock wave heats the air.
• The heated air mixes with hydrogen (cold) at contact surface and ignition occurs. Wolanski and Wojcicki (1972): A
diffusion ignition mechanism.
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Prevention of Ignition Source

• Ignition sources must be eliminated or isolated in appropriate way and operations should be conducted as if
unforeseen ignition sources could occur.

• Grounding methods should be evaluated to minimize the risk of static discharge and the potential for lightning strikes
in outdoor environments

• Materials selected for the use in hydrogen environments should be evaluated for their ability to discharge static
electricity. Insulation materials such as wood, paper, and some fabrics will typically form a conductive layer that can
prevent static build up by absorbing water from the air in environments where the relative humidity is greater than
50%. Where humidity can fall below this level, care must be taken to avoid using insulating materials.

• Recommended practices for grounding methods to prevent static discharges can be found in various national and
international standards that cover the installation of electrical equipment in hazardous environments

• Electrical equipment selected for use in hydrogen environments can also be a source of sparks or heat generation,
and care should be taken to follow the appropriate national and International Electrical Standards for installation.
Explosion proof devices could be warranted in some contained environment.
 FIRE SAFETY FOR HYDROGEN

Other Precautions

Actions should be taken to prevent hydrogen leakage from high pressure containment as leakage in high velocity could
actually be its own potential source of ignition and fuel.

Selection of materials
It is also a common knowledge that hydrogen atoms are so small that they can diffuse into the grain boundaries of
carbon steels and low alloys steel in the right condition. Therefore utmost care must be given to the selection of
materials for distributing or storing hydrogen and the safety factor allowance used in design.

Many engineering alloys experience a degradation of properties when used in high pressure hydrogen service. The
generic term for this is hydrogen embrittlement. The effects can range from a reduction in tensile strength and ductility
to a marked increase in the rate of fatigue crack growth. Elevated temperatures also can be problematic, promoting
hydrogen attack in carbon and low-alloy steels.

Austenitic (300 series) stainless steels meeting the temperature limits of ASME B31.12 are recommended for liquid and
gaseous hydrogen product piping, tubing, valves, and fittings. The most stable grade is Type 316/316L. Type 316/316L is
relatively immune to hydrogen embrittlement when exposed to high pressure hydrogen and is preferred over other
grades such as Type 304L and Type 321. When available, austenitic stainless steels should be used in the annealed
condition.
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Other Precautions

Selection of materials

Carbon steel usually is limited to gas service at operating temperatures equal to or greater than –20 °F (–29 °C). Carbon
steels meeting the temperature limits of ASME B31.12 may be used for gaseous hydrogen product piping, tubing, valves,
and fittings.

For high pressure applications, carbon steel shall be used with caution. Carbon steels with high-carbon content and high-
strength, low-alloy carbon steels are susceptible to embrittlement and crack propagation. The use of carbon or alloy
steels requires control of tensile strength, heat treatment, microstructure, and surface finish as well as initial and
periodic examination for inclusions and crack-like defects when in cyclic service.

For high temperature applications, the suitability of carbon or low-alloy steel shall be evaluated using the “Nelson
charts” in American Petroleum Institute (API) RP 941, Steels for Hydrogen Service at Elevated Temperatures and
Pressures in Petroleum Refineries and Petrochemical Plants for resistance to embrittlement. Carbon steels with higher
strength levels (as defined in the API RP 941 “Nelson charts”), high-carbon, and low-alloy content are more susceptible
to hydrogen embrittlement, and their use should be thoroughly investigated.

Piping, tubing, valves, and fittings made of gray, ductile, or malleable cast iron shall not be used in hydrogen service.
 FIRE SAFETY FOR HYDROGEN
Other Precautions

Selection of materials and design

Also design of blowdown valves shall take careful consideration to ensure that the exit velocity would be reduced by the
time hydrogen gas leaves to mix with surrounding air to prevent heating up of air caused by shock waves formed.

Selection of flame arrestor material is also important to ensure that there is NO expedited corrosion due to interaction
of hydrogen with materials. Corroded flame arrestor will not be able to function properly.
 FIRE SAFETY FOR HYDROGEN
FIGHTING HYDROGEN FIRE

• Only properly trained and equipped firefighters should attempt to fight or manage a hydrogen fire.
• Normally hydrogen fires are not extinguished until the supply of hydrogen has been shut off or exhausted since there
is a danger of re-ignition and explosion. Personnel who work around hydrogen should be trained in the characteristics
of hydrogen fires and proper procedures for dealing with them.
• In general, personnel should be trained to evacuate and assist other persons and call first responders but not to
actually attempt to fight a fire.
• Since hydrogen has a very wide flammability range and low ignition energy, it should be assumed that any hydrogen
leak or release is likely to result in hydrogen fire.
• Since hydrogen is colorless, odorless, burns with a nearly invisible flame (especially during daylight hours), and gives
off relatively little radiant heat, a hydrogen fire is often difficult to detect. Thermal imaging cameras and flame
detectors should be used to verify that a hydrogen flame is present. If these tools are not available, personnel should
cautiously approach a suspected leak and watch for thermal waves that signal the presence of a flame and put small
amount of combustible objects (e.g. a broom) or dust particles into the suspected flame to detect its presence.
• Water can be used to fight hydrogen fire by cooling down the container of the hydrogen or cooling down the fuel.
• Hydrogen is lighter than air and can diffuse very fast. Thus it is very important to note the wind condition when
dealing with hydrogen leakage and fire. DO NOT STAND IN WINDWARD DIRECTION WHEN FIGHTING FIRE.