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Hydrogen Safety
Fundamentals
Sarah Eck, P.E., CCPSC ■ Michael D. Snyder, P.E. ■ DEKRA Process Safety

As the number of producers and end-users of hydrogen grows,


so too does the importance of its safe handling and use.

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.

Establishing a basis of safety


All fuels are associated with some degree of danger and p Figure 1. A self-sustaining combustion reaction requires a fuel, an oxidant, and
can cause a safety incident if not handled properly. The most an ignition source. At normal pressure and temperature, removing one side of the
common hazard associated with hydrogen is its propensity fire triangle prevents combustion from occurring.

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Copyright © 2021 American Institute of Chemical Engineers (AIChE).
Not for distribution without prior written permission.
coupled with a low minimum ignition energy (Figure 2). ever, the rate of hydrogen generation can accelerate under
The relatively high laminar burning velocity of hydrogen-air certain process upset conditions, or as a result of an operator
mixtures also represents a significantly large consequence error, in a way that exceeds the design limits of the equip-
potential from fire and explosion scenarios. The laminar ment and other safety mitigations.
burning velocity influences the sizing of deflagration vents Facilities must engage in robust hazard analysis with
for enclosures and overpressure calculations involving multidisciplinary teams to consider what process upsets or
unconfined vapor cloud explosions (VCEs). mitigation failures may cause situations with intolerable risk,
Enclosures and spaces that may contain hydrogen (like and what additional mitigations are needed. For example,
other fuels) will require adequate ventilation and purging on the night of May 3, 2019, an explosion occurred at the
to maintain the atmosphere below the lower flammability AB Specialty Silicones facility in Waukegan, IL. The facil-
limit (LFL) so that the space is too fuel-lean to ignite. Note ity processed silicone hydride emulsions, which are known
in Figure 2 that although hydrogen has a wide flammabil- to react to form hydrogen when mixed with strong acids
ity range, its LFL is higher than that of other common fuels and bases, or if the material is heated to high temperatures.
such as propane and gasoline vapor. The U.S. Chemical Safety and Hazard Investigation Board
As with other common fuels, if a continuous stream of (CSB) investigation concluded that an unintended chemical
hydrogen ignites while it is being released under pressure, reaction occurred in a batch reactor when an incompatible
a jet fire may result. These flames can be nearly invisible chemical was unintentionally pumped into the vessel. This
when dust or soot are not present, so fires can burn unde- unintended chemical reaction produced hydrogen gas in
tected if sensing equipment is not being used. The pressure equipment that could not contain the pressure. The hydro-
at which hydrogen is released and the size of the hole deter- gen escaped the equipment and ignited within the building,
mine the size of the jet fire. For this reason, many codes and resulting in an explosion that killed four people and seri-
standards recommend flame detection equipment installa- ously injured one (3).
tions that alert personnel to prevent them from inadvertently The hazard analysis process should also consider a slow
contacting the flame. If the hydrogen release does not accumulation of hydrogen that could occur over time in an
immediately ignite, precautions must be taken to address enclosed space, for example, in a battery charging room.
the potential explosion hazards, especially in congested or If the ventilation fan in the battery charging room has an
enclosed spaces. outage, it may lead to an accumulation of an explosive level
Liquified hydrogen use presents the typical haz- of hydrogen in the room; if no detection instrumentation is
ards associated with handling cryogenic fluids. Several present, operators may be unaware of the hazard.
respected suppliers of cryogenic fluids provide complemen- In the specialty chemical and pharmaceutical industries,
tary safety resources, such as Air Products’ Safetygram 16,
“Safe handling of cryogenic liquids” (2). Cryogenic burns
80 0.35
are a potential risk, and if a cryogenic liquid is released, it 75.0%
can hover at ground level until it expands as it warms. This
70 0.29
phenomenon can rapidly displace air in a space without 0.30

warning, because hydrogen is both odorless and color- 0.26


60
less. In spite of this property, hydrogen is nontoxic, and 0.24 0.25
Flammable Range, % in Air

in outdoor systems the gas rapidly disperses and rises into


Ignition Energy, mJ

50
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.

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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

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Copyright © 2021 American Institute of Chemical Engineers (AIChE).
Not for distribution without prior written permission.
change, and conduct quality assurance activities to ensure
that the proper materials are installed to avoid piping, gas- Many contractors, manufacturing workers,
keting, or vessel failure (6). and engineers are familiar with protecting
Human factors hazards. Hydrogen’s low density can plants from heavier-than-air hydrocarbon
cause concerns in confined spaces, enclosed processing
equipment, and within process buildings. Unlike hydro­ vapors but are unfamiliar with “looking up” to
carbon vapors that are heavier than air and sink to low identify fire and explosion hazards.
points, hydrogen releases rise and can accumulate at high
points such as building rooflines, high-point piping, and numerous resources that explain these principles, which are
sewer dead legs. not unique to facilities that store or transfer hydrogen.
Many contractors, manufacturing workers, and engineers An additional way to help manage risk is to assign
are familiar with protecting plants from heavier-than-air experts to participate on hazard analysis teams and review
hydrocarbon vapors but are unfamiliar with “looking up” to boards that manage facility change. These team members
identify fire and explosion hazards. Be mindful that work- must know current revisions and understand how to imple-
ers may be unaware of the risk associated with hydrogen ment the codes, standards, and good engineering practices
accumulation. When conducting maintenance and non- associated with hydrogen used at their facility. Codes and
routine work, additional measures and robust work processes standards establish the minimum requirements to protect
may be necessary to aid in hazard recognition and ensure workers and other structure occupants, the neighboring
that a thorough job safety analysis is completed before the public, and first responders. Many of these recognized and
work is performed. Facilities must establish adequate hazard generally accepted good engineering practices are available
awareness onboarding programs and governance systems to online for free or at a low cost. Currently, a multitude of
ensure that all workers understand that the buoyant nature of resources are available in the U.S. and Canada through the
hydrogen can introduce risk in areas of the plant they are not Hydrogen Tools Portal, which was developed by the Pacific
accustomed to reviewing. Northwest National Laboratory with support from the U.S.
Common hazards discovered in field audits and human Dept. of Energy’s Office of Energy Efficiency and Renew-
factors assessments may include finding ceiling-mounted able Energy (EERE) (8).
electrical devices that are not intrinsically safe; hot-work A few helpful sources of information include the
permits that are issued without testing atmospheres at the following:
high-point traps within equipment or enclosures; failure • International Building and Fire Code Requirements
to provide ventilation; or failure to design piping that does • CGA H-3, “Cryogenic Hydrogen Storage”
not have piping dead legs or high points that can form a • National Fire Protection Association (NFPA) 2,
pocket of hydrogen accumulation. Although these measures “Hydrogen Technologies Code”
seem fundamental, incidents have occurred due to a lack • NFPA 55, “Compressed Gases and Cryogenic Fluids
of hazard awareness, as demonstrated in an October 2011 Code”
Waxahachie, TX, process upset and fire. A facility was • ISO 19880-1, “Gaseous Hydrogen – Fuelling stations”
destroyed when hydrogen ignited and the fire spread to • FM Global Datasheet No. 7-91, “Hydrogen.”
nearby ignitable materials, which were not properly isolated It is important to remember that many federal and local
or separated. The U.S. Occupational Safety and Health governments require that facilities that handle hydrogen are
Administration (OSHA) cited the facility for inadequate designed and maintained to meet certain revisions of certain
ventilation and failing to conduct a hazard assessment (7). codes, standards, and good engineering practices. It is also
important to follow any risk management practices required
Technical aspects of identifying hazards by the facility’s insurance carrier. Additional resources can
and managing risk be obtained by accessing the Center for Hydrogen Safety at
Identifying process hazards and managing risk is a three- www.aiche.org/chs.
step process: Regardless of the industry involved or application, there
1. Establish and maintain process safety information that are common mitigations that organizations leverage. A few
is important to understanding the design basis of the system. of these measures are mentioned below.
2. Conduct hazard identification and risk analysis on Safety by design. Process designers should consider
the facility when managing change and when conducting how to make the situation inherently safer by limiting the
permitted work. volume of hydrogen inventory stored in one place and
3. Implement and maintain safety controls. eliminating scenarios where it can cause an explosion. An
The Center for Chemical Process Safety (CCPS) provides example of a way to make a situation inherently safer is

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must be ventilated with systems that have reliable air flow


detection alarms. Ventilation should focus on high points,
Fixed flammable gas and flame detectors such as the roofline, where hydrogen can accumulate. Per
NFPA 91, “Standard for Exhaust Systems for Air Convey-
are recommended for facilities that
ing of Vapors, Gases, Mists, and Particulate Solids, (2020
transfer and store bulk hydrogen. Edition),” ventilation should be designed to maintain the
concentration of hydrogen below 25% of the LFL and
equipment should be routinely tested to ensure it is operat-
to locate the storage and transfer equipment outside and ing to that design basis.
to avoid enclosing equipment in a shed or building. It is Purging and inerting equipment. The limiting oxygen
important to eliminate traps and dead-legs in piping and concentration of hydrogen is low and the flammable limits
vents where hydrogen is transferred. The materials of con- are wide. This presents unique concerns when equipment
struction of any part of the system that comes into contact is open to the air before or after a hydrogen transfer. Safety
with hydrogen should be thoroughly evaluated; material incidents have occurred in the past because equipment was
compatibility is closely tied to the operating conditions such not adequately inerted with nitrogen prior to use, or a man-
as pressure and temperature. ual powder addition introduced air into the system, resulting
Inventory management and facility spacing. Although in an explosion. It is not uncommon for some facilities to
facilities often try to design systems so that they will pre- establish unique inerting or purging procedures that have
vent a fire or explosion, the facility must be designed with undergone robust hazard analysis and are controlled through
the assumption that ignition can occur to help minimize safety systems or controls. Follow the guidance in NFPA 69,
the impact of primary and secondary fires and explosions. “Standard on Explosion Prevention Systems,” to calculate
Bulk inventories of hydrogen must be located with respect the appropriate measure to take to purge and inert equipment
to surrounding facility buildings and units to help limit to recommended safe levels (9).
risk to the surrounding facility and personnel. Minimum Ignition source management. Manage ignition sources
separation distances of bulk gaseous hydrogen inventories via bonding, grounding, and ensuring that electrical devices
that are provided in both NFPA 2 and NFPA 55 consider meet applicable hazardous area classification require-
unignited and ignited jet flames of hydrogen at various ments. A robust hot-work program must be implemented
pressures. The characteristics of the jet flame will depend and enforced. The program must consider precautions to
on the effective leak diameter and pressure of the leak, so adequately purge and ventilate high-point traps, and then
considerations must be provided for the specific situation include a step to sample the atmosphere before work starts.
in which bulk hydrogen is used and transferred. Additional Ceiling-mounted equipment should be inspected to ensure
details are provided in NFPA 2, Appendix E. Ideally, the that it meets the hazardous area classification requirements
facility layout and explosion venting should be config- of NFPA 497, because many facilities that typically handle
ured so that personnel and other parts of the facility will hydrocarbon vapors do not require installation of classified
not be harmed should an incident occur. In some situa- equipment at those elevations.
tions, additional control measures may include protecting Leak and flame detection systems. Fixed flammable
or reinforcing buildings to withstand blast pressures that gas and flame detectors are recommended for facilities that
may be generated in an explosion. In these situations, an transfer and store bulk hydrogen. Flammable gas detectors
engineering analysis may be required in conjunction with must be placed so that they can sense likely leak points of
a hazard analysis to assure that the design meets company hydrogen. Typically, they are mounted at high points within
risk tolerance. rooms and near ventilation intakes. Flame detection systems
If hydrogen is ignited during a release, a critical mea- are necessary because hydrogen jet fires can be nearly invis-
sure to help mitigate the situation is to isolate the supply ible. Detectors need to provide information to a continuously
from the leak point. It is not unusual for facilities to install staffed control room and/or automatically initiate a shut-
multiple remote stations or push buttons for workers to down sequence to set the process into a safe state.
activate a shut-down sequence that quickly closes isola- Human factors assessments. Employees and contractors
tion valves located at the tank. In most instances, a jet fire should be trained on and understand operations with high-
should not be extinguished until the supply source of the risk potential and the human-factors controls that help error-
leak is contained to prevent potential hydrogen accumula- proof the work environment. Workers should conduct a field
tion and explosion. tour of critical aspects of the work that will be performed,
Ventilation. Hydrogen systems are often located and they should be able to recall the locations of hazards
outdoors to avoid explosion concerns. Enclosed rooms and how to correctly perform tasks. The key is to provide

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an opportunity for personnel to understand what to do, why of the process and the organization managing the risk. It is
they do it, and how, as these activities help personnel com- unique from other legal requirements in that it introduces
mit important concepts to memory. a set of management systems in addition to organizational
In addition to hazard awareness training, implement culture and competency-building components. The program
checklists that include critical steps for certain kinds of includes mechanisms to adopt the codes and standards previ-
activities to help prevent missed or skipped steps, such as ously mentioned in this article, and it helps to:
testing high points in confined spaces prior to conducting • build the competency and skill development of all staff,
hot work. Management of change (MOC) protocols should including frontline workers, their supervisors, and technical
include checklists with expertise review to confirm that support personnel
changes align with codes and standards, and to evaluate the • build a strong facility culture that is cognizant of the
change for potential unintended consequences that could explosive properties of hydrogen and willing to stop work if
result in a safety event. conditions seem unsafe
• implement robust management systems that establish
Embracing a risk-based process safety program a technical basis of safety, hazard identification and risk
The technical aspects of avoiding risks are important, but assessments, safe work practices, emergency procedures,
they cannot be implemented effectively without developing operational excellence around procedures, and a robust asset
organizational competency, culture, and management sys- integrity program. CEP

tems. Even when managing small inventories of hydrogen,


organizations must be diligent to avoid complacency.
Many facilities that manage smaller inventories of Literature Cited
hydrogen, or manage inventories of material that can form
1. Hydrogen Tools, “Hydrogen Fuel Cell Codes & Standards,”
hydrogen as a byproduct, fall outside of the boundaries of H2 Tools, https://h2tools.org/codes-standards (accessed
a legal requirement to implement a process safety manage- Oct. 26, 2021).
ment program. Facilities that best manage their risk rec- 2. Air Products, “Safe Handling of Cryogenic Liquids,” Air
ognize the importance of developing work processes and Products Safetygram 16, https://www.airproducts.com/-/media/
airproducts/files/en/900/900-13-079-us-safe-handling-of-cryo-
robust management systems at their facilities. CCPS offers liquids-safetygram-16.pdf (accessed Nov. 7, 2021).
complementary resources to implement a risk-based process 3. U.S. Chemical Safety and Hazard Investigation Board,
safety program that can be scaled based on the complexity “Chemical Reaction, Hydrogen Release, Explosion and Fire
at AB Specialty Silicones,” Report No. 2019-03-I-IL, www.csb.
gov/ab-specialty-silicones-llc (Sept. 24, 2021).
SARAH ECK, P.E., CCPSC, is a Senior Process Safety Engineer at 4. U.S. Chemical Safety and Hazard Investigation Board,
DEKRA North America, a global testing, consulting, and certification “Tesoro Refinery Fatal Explosion and Fire: Catastrophic Rupture
company. Her career includes roles in manufacturing, environmental, of Heat Exchanger, Investigation Report,” https://www.csb.gov/
health, and safety (EHS), and process safety at Eli Lilly, Stepan Co., tesoro-refinery-fatal-explosion-and-fire (Apr. 2, 2010).
Hemlock Semiconductor, and Corteva Agrisciences. In addition, she
serves on the technical committee for the National Fire Protection 5. Hydrogen Tools, “Lessons Learned,” Pacific Northwest National
Association (NFPA) 401, “Recommended Practice for the Preven- Laboratory Through Support with U.S. Dept. of Energy’s Office
tion of Fires and Uncontrolled Chemical Reactions Associated with of Energy Efficiency and Renewable Energy (EERE), https://
the Handling of Hazardous Waste,” and she contributes to CCPS h2tools.org/lessons (accessed Aug. 13, 2021).
Project 276, “Guidelines/Essentials of Safe Work Practices.” She has
a bachelor’s degree in chemical engineering from Purdue Univ. and 6. Factory Mutual, “FM Global Hydrogen Datasheets (online):
is both a Professional Engineer and Certified Process Safety Profes- Hydrogen, Data Sheet ID# 7-91,” www.fmglobal.com/research-
sional (CCPSC). and-resources/fm-global-data-sheets (Apr. 2021).
MICHAEL D. SNYDER, P.E., CSP, CFPS, is the Operational Risk Man- 7. Occupational Safety and Health Administration, “U.S.
agement Practice Vice President for DEKRA North America. He was Department of Labor’s OSHA Cites Magnablend for Serious
previously the Global Director of Safety and Loss Prevention for Violations Following Chemical Fire at Waxahachie, Texas,
Dow Corning Corp., responsible for leading the company’s occu- Facility,” OSHA News Release – Region 6, 12-557-DAL,
pational and process safety programs. He currently serves on the https://www.osha.gov/news/newsreleases/region6/03302012
Center for Chemical Process Safety (CCPS) Advisory Board and is a
former member of the National Fire Protection Association (NFPA) (Mar. 30, 2012).
Standards Council. He is also a technical committee member of 8. Hydrogen Tools, “Codes and Standards,” Pacific Northwest
NFPA 30, “Flammable and Combustible Liquids Code,” NFPA 1, “Fire National Laboratory Through Support with U.S. Dept. of Ener-
Code,” and NFPA 1720, “Standard for the Organization and Deploy- gy’s Office of Energy Efficiency and Renewable Energy (EERE),
ment of Fire Suppression Operations, Emergency Medical Opera-
tions and Special Operations to the Public by Volunteer Fire Depart- https://h2tools.org/fuel-cell-codes-and-standards?search_api_full-
ments.” Snyder earned a bachelor’s degree in chemical engineering text= (accessed Aug. 13, 2021).
from Cornell Univ. and a master’s degree in occupational safety and 9. National Fire Protection Association, “NFPA 69: Standard on
health from Columbia Southern Univ. He is a registered professional Explosion Prevention Systems, 2019 Edition,” www.nfpa.org/69
engineer in Michigan, a Certified Safety Professional (CSP), and a
Certified Fire Protection Specialist (CFPS). (accessed Nov. 10, 2021).

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Not for distribution without prior written permission.

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