Professional Documents
Culture Documents
Hydrogen Safety
Fundamentals
Sarah Eck, P.E., CCPSC ■ Michael D. Snyder, P.E. ■ DEKRA Process Safety
H
ydrogen use has dramatically increased in recent to ignite. All engineers are familiar with the fire triangle and
years, especially as it has grown in popularity as a the idea that three conditions must be present to sustain com-
transportation fuel. Although hydrogen has been used bustion: an oxidant (often air), fuel, and an ignition source
in industry for decades, its use as a fuel for vehicles or for (Figure 1). Establishing a basis of safety for this hazard
stationary power generation in consumer environments is requires understanding the fuel properties and preventing
relatively new (1). Hydrogen is traditionally used to make situations where the three combustion conditions are present.
ammonia for fertilizer, remove sulfur in fuels in oil-refining Hydrogen is unique from other ignitable vapors and
processes, manufacture silicon chips, and hydrogenate oils in gases because it has unusually wide flammability limits
the food industry. It is also a common reactant and byprod-
uct in the specialty chemical and pharmaceutical industries.
Many chemicals have inherent risks that must be man-
aged, and hydrogen is no exception. If managed appropri-
ately, hydrogen can present less risk than other fuel sources.
For example, hydrogen is nontoxic. And, because hydrogen
is lighter than air, it dissipates rapidly when it is released,
unlike hydrocarbon-based fuels. However, although it is a
commonly used and understood molecule, hydrogen pres-
ents unique safety challenges. Therefore, it is important for
every engineer and facility support specialist to know and
understand how to identify and mitigate hazards presented
by hydrogen.
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the atmosphere. 0.20
40
Hazards of hydrogen
0.15
Many resources are available that explain the properties
30
and hazards of hydrogen. In the chemical process indus-
tries (CPI), experts should be consulted to ensure that the 0.10
20
equipment design, mitigation, and administrative systems 15.0%
that support the process are appropriate for the risks that 10.1% 0.05
10 7.6%
are present. 5.0% 4.0% 0.02
2.1%
Reactive chemistry concerns. Hydrogen is a byproduct of 1.4%
0.00
0
many chemical processes, including battery charging opera- Natural Gas Propane Gasoline Vapor Hydrogen
tions, reactions of metal dusts in water, and batch processing
operations that involve organic chemistry. Often, typical p Figure 2. Hydrogen’s flammability range is larger than other fuels. In addition,
operations do not present a fire or explosion hazard. How- hydrogen takes very little energy to ignite.
hydrogen is sometimes used as a reactant, or hydrogen may high processing temperatures that are above 400°F (4).
be formed as a byproduct during processing. These chemi- The failure mechanism of HTHA depends on several
cal reactions can have energetic behavior that poses an factors that require expert review to ensure continued safe
overpressure hazard during process upsets. Overpressure operation of equipment. Internal or outside experts who
scenarios are not unique to hydrogen, and venting non understand how to leverage inspection data with operations
reactive systems can be addressed through standards such history should conduct an analysis and recommend changes
as the Compressed Gas Association’s (CGA’s) G-5.5. in equipment design and testing procedures if hydrogen
Codes and standards often recommend that intended hydro- attack could occur. This expertise should also be leveraged
gen discharges to the atmosphere be vented at a sufficient during capital project work and when managing change to
height and location such that radiant heat will not harm explore inherently safer measures that avoid risk. Resources
personnel or property. such as API (RP) 941, “Steels for Hydrogen Service at
However, systems that involve chemical reactions pose Elevated Temperatures and Pressures in Petroleum Refiner-
unique hazards that these standards do not address. Chemi- ies and Petrochemical Plants,” can be leveraged to identify
cal reactions should be screened for runaway potential and hazards and material performance concerns.
the vessel emergency pressure relief should be sized using Facility staff should also be aware of hydrogen embrittle-
Design Institute for Emergency Relief Systems (DIERS) ment within metals, a damage mechanism in which hydrogen
methodology to address a worst-case overpressure scenario. penetrates the metal lattice of (typically) iron-based and
Relief sizing can be a challenge because the effluent must nickel-based alloys. This mechanism can increase the risk of
be discharged to a safe location and both the jet fire and catastrophic brittle fracture of the metal. The rate and amount
explosion hazards must be considered. Typically, facilities of material deterioration is a function of the material type
that will deal with chemical reactions need to partner with a and properties, process conditions, and mechanical stress-
development chemist or qualified laboratory to understand ors involved. To avoid the risk associated with hydrogen
the runaway reaction hazards and determine an appropriate embrittlement, it is important to carefully follow engineer-
design for their emergency pressure-relief systems. ing recommendations for material selection and to instate a
Common scenarios that may cause a runaway reaction robust asset integrity testing and inspection program.
include adding the rate-limiting ingredient too quickly, add- Material selection in hydrogen service is often over-
ing too much catalyst, intermittently turning a batch agitator looked because the failure mechanisms involving hydrogen
on and off (i.e., jogging the mixer), or overheating a vessel. can be complex and often require expertise to identify how
If screening tests identify energetic behavior, additional data seemingly subtle details can impact material performance.
may need to be collected to help size emergency pressure Additionally, many facilities are unaware of lessons learned
relief or aid in the design of other mitigation systems. by those outside their company. Potential learnings are
Mechanical integrity challenges. On April 2, 2010, often put forward by NASA, smaller scale laboratories,
a carbon steel heat exchanger ruptured at a petroleum fuel stations, and petroleum refineries. These safety lessons
refinery, killing seven workers. The cause of the equipment can be relevant to any operation that uses hydrogen and
failure was high temperature hydrogen attack (HTHA), can also be applied to facilities with different technology.
a damage mechanism that results in cracking and other The online Hydrogen Tools Portal (https://h2tools.org)
defects within steel. HTHA occurs in high stress areas contains dozens of case studies that share lessons learned
within piping and vessels, and it is more likely to occur at through many industries, including a page devoted to
incidents caused by material compatibility. The portal
offers a link to Sandia National Laboratories’ web-based
Hydrogen Quick Facts resource that summarizes research and information from
• Small molecule that migrates quickly
technical reports regarding hydrogen’s impact on materials
through openings and many polymeric of construction (5).
materials (e.g., plastics) Besides HTHA and hydrogen embrittlement, engineers
• Less dense than air (rises)
should be aware of several other mechanical integrity chal-
lenges when selecting and maintaining equipment. Elasto-
• Low ignition energy (0.016 mJ)
mer and gasketing materials must be carefully selected for
• Wide flammability limits (4–75% in air) the operating pressure and temperatures to ensure adequate
• Low limiting oxygen concentration (5%) sealing surfaces, as hydrogen can diffuse through some
• White/invisible flame that is hard to detect when dust or materials. Contact a mechanical integrity expert to assess
other contaminants are not present what maintenance and operational measures are neces-
sary to assure proper material selection, carefully manage