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Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

4.8 HYDROGEN SAFETY

4.8.1 INTRODUCTION

The major hazard associated with the handling and use of hydrogen is flammability. This
section addresses hydrogens flammability hazard by establishing basic requirements and
procedures for safe handling and use of gaseous hydrogen. The requirements in this section
are based on Occupational Safety and Health Administration (OSHA) regulation 29 CFR
1910.103, "Hydrogen," the National Fire Codes published by the National Fire Protection
Association (NFPA), and BOCA National Fire Prevention and Building Codes.

The requirements in this section must be followed when designing, installing, maintaining, or
operating apparatus or facilities involving hydrogen use. These requirements must be applied to
experimental operations and processes and may or may not be applicable to specialized
applications such as hydrogen/oxygen torches whose use is governed by the open flame permit
program. If users have any doubt as to whether or not a particular requirement should be
applied to a specific situation, they should contact a hydrogen safety specialist for guidance.

The term "hydrogen use" in this section encompasses the handling, use, and storage of
gaseous hydrogen. This section does not cover the handling and use of liquid hydrogen.
Contact the PFS-FEC Fire Protection for assistance if use of liquid hydrogen is planned.

4.8.2 POINT OF CONTACT

If you have questions on the content of this section, please contact T. Tess, EQO-SPC, at
2-6183.

4.8.3 RESPONSIBILITIES

Division directors and department heads (DD/DH) must:

Designate authorization levels for hydrogen use;

Provide a safety review process for proposed hydrogen use; and

Ensure hydrogen use is authorized only after confirming that the requirements of this
section have been met.

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Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

Line supervisors responsible for activities involving hydrogen use must, prior to initiating
such activities:

Ensure the requirements in this and other applicable sections (see 4.8.15) are followed
(including design, installation, maintenance, and operation);

Consult PFS-FEC whenever operations involve a high hazard such as use of bulk
storage of hydrogen gas, liquid hydrogen, detonable gas mixtures, or high-pressure or
high volume operations (>15 psi or >10 lpm);

Consult PFS-FEC whenever operations involve the use of potentially incompatible

materials, such as plastic tubing, in hydrogen gas distribution systems;

Perform or initiate a safety review for new or modified hydrogen use;

Train their personnel;

Designate qualified persons for specific hydrogen use operations;

Ensure the preparation of, and approve, written operating and emergency procedures;

Control access to hydrogen use areas;

Ensure that warning signs are posted (see 4.8.12);

Ensure written instructions are posted at each bulk storage facility (see 4.8.11); and

Consult an industrial hygienist when safety review determines this is necessary.

The Plant Facilities and Services Division must provide services and resources, such as the
availability of a fire protection engineer knowledgeable in fire hazards analysis, to assist in the
performance of safety reviews and the interpretation of codes and regulations applicable to
hydrogen safety.

4.8.4 DEFINITIONS

flammable range - maximum and minimum concentrations of a fuel (gas or vapor) in an

oxidizer (gas or vapor) at which flame propagation can occur. Gaseous hydrogen has a
flammable range in air of approximately 4% to 75% by volume.

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 Page 3 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

hydrogen use - encompasses the handling, use, and storage of gaseous hydrogen.

lower flammable limit - also known as lower explosive limit or LEL; the minimum ignitable
concentration of a flammable gas in a standardized test apparatus. This measurement varies
depending on temperature, pressure, and intensity of the ignition source, as well as on the
specific gas mixture being tested. Accordingly, LELs should be used with caution since they do
not necessarily reflect the actual limits of ignitability as they may exist in an experimental
apparatus or situation. Hydrogen can detonate (explode at supersonic velocity) in air over a
range of about 18% to 59% by volume.

minimum ignition energy - the minimum energy required for the ignition of a particular
flammable mixture in a standardized test apparatus at a specified temperature and pressure.
The minimum ignition energy of hydrogen is 0.02 millijoule, an order of magnitude less than that
of hydrocarbons. For example, methane gas has a minimum ignition energy of approximately
0.28 millijoule. Gaseous hydrogen can be ignited by an almost imperceptible spark or by static
electricity discharge.

qualified person - a person who has been made aware of the hazards of hydrogen, has been
trained in the safe operation of facilities containing hydrogen, and has been instructed on the
procedures to be followed in emergencies.

4.8.5 PROPERTIES OF HYDROGEN

Hydrogen is a colorless, odorless, tasteless, flammable nontoxic gas. It is the lightest gas
known, having a specific gravity of 0.0695 (air = 1.0). Although hydrogen can act as an
asphyxiant by displacing air, the major hazard associated with handling hydrogen is
flammability. This section does not address hydrogen acting as an asphyxiant. Consult an
industrial hygienist for guidance on asphyxiant hazards.

Hydrogen burns with an almost invisible (nonluminous) flame.

Hydrogen diffuses rapidly in air and through porous materials and can dissolve in and diffuse
through metals. It may leak out of a system that is gas-tight with respect to air or other common
gases at equivalent pressure.

Hydrogen has a weakening effect (hydrogen embrittlement) on steel and other metals such
as nickel and copper-nickel alloys.

Hydrogen discharging from high pressure to low pressure is heated and has been known
to self-ignite. Therefore, cracking a valve on a hydrogen container to remove dust or dirt from

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 Page 4 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

fittings is prohibited. To eliminate the need for venting, hydrogen cylinders must be equipped
with a protection plug at the gas outlet.

4.8.6 SAFETY REVIEWS

All experiments and operations involving the storage, use, or generation of hydrogen
must undergo a documented safety review in accordance with ES&H Manual Section 21.2,
Experiment Safety Review. These reviews must specifically address

Compliance with the requirements of this section;

Compliance with applicable codes and standards including NFPA 45, NFPA 50A, and
NFPA 101; BOCA National Building Code, Section 307; and 29 CFR 1910.103, as
required by DOE Order 420.1, Facility Safety;

Equipment construction; operating parameters and procedures, and operator

training/qualifications;

Hazards and failure modes; safe operating envelope; recognition of adverse conditions;
and any impacts related to adjacent or exposed operations and experiments; and,

Emergency notification; emergency shutdown; and emergency response procedures.

4.8.7 LOCATIONS

Hydrogen must be stored, routed through, used, or generated only in division-approved

locations. In general, approved locations must be protected by sprinklers in accordance with
NFPA 13 and must provide either sufficient ventilation to ensure that an explosive gas
concentration cannot develop, or other approved means of ensuring that a leak or release does
not create an imminent danger. PFS-FEC Fire Protection should be consulted if there is any
doubt as to whether or not a particular requirement should be applied to a specific situation.

Hydrogen cylinders or experimental apparatus must not be located within three feet of
any required exit unless a noncombustible partition is provided between the hydrogen
equipment and the egress path.

The area within 20 feet of a hydrogen container must be kept free of stored flammable
materials and oxidizing gases.

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 Page 5 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

4.8.8 GENERAL FIRE SAFETY

Line supervisors must ensure that combustibles and ignition sources are evaluated in
the safety review and controlled in all areas where hydrogen may be present. Potential
ignition sources include static electricity; self-heating, spark-generating electrical equipment
(e.g., motors, unsealed switches, duplex electrical outlets); tools other than nonsparking tools;
hot surfaces (including lights, furnaces, hot plates, dryers, etc.); engines; vehicles; and open
flames of any kind. When determined by the safety review to be necessary, electrical
equipment must comply with NFPA 70, National Electrical Code, Article 501, as applicable.
HVAC equipment must be suitable for the actual hazards present.

In many cases it is more practical to prevent an explosive atmosphere from developing than it is
to eliminate all potential ignition sources. Emphasis on confining leaks and providing adequate
ventilation will reduce the need for special electrical equipment. When in doubt, users should
consult with a PFS-FEC fire protection engineer.

An accumulation of static electricity can cause an electrostatic discharge to jump

between two pieces of equipment. The energy of the electrostatic discharge may be
sufficient to ignite any hydrogen present. The safety review must address this potential in the
final set up. When the safety review determines it is necessary to reduce the risk of ignition,
specified transport, storage, and transfer system equipment and connections must be
grounded. In addition, the safety review must determine which metal components of a hydrogen
system must be electrically bonded and grounded, including tanks, regulators, valves, pipes,
vents, etc.

The preferred method for extinguishing a gaseous hydrogen fire is to turn off the gas
supply and allow the hydrogen flare to burn itself out, because uncontrolled hydrogen leaks
pose severe explosion hazards. Exposed surfaces should be cooled with copious quantities of
water, particularly those directly impinged by flames. Only qualified firefighters in full turnout
gear should be allowed in the fire zone; all other personnel should be evacuated.

Lightning protection must be provided for facilities handling or storing hydrogen in

accordance with ES&H Manual Section 19.3, Lightning Protection.

4.8.9 LIMITING HAZARDS

Quantities of hydrogen used and/or stored must be limited and excess hydrogen cylinders
must be stored in a division-approved location. Users must comply with the applicable
requirements of ES&H Manual Section 13.2, Compressed Gas Cylinders.

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 Page 6 of 11

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Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

Allowable Inventory. Section 13.2 allows up to four (4) standard cylinders of flammable gas
(approximately 200 cubic feet capacity each) in a sprinklered laboratory. Up to eight (8)
standard cylinders of flammable gas are allowed in a sprinklered laboratory where all of the
cylinders in use are enclosed in flammable gas cabinets or other exhausted enclosures and the
number of cylinders that are not in use or not installed in flammable gas cabinets or other
exhausted enclosures does not exceed four (4). For the purposes of this section, a cylinder is
considered to be "not in use" when the regulator has been removed and the safety cap
installed.

Experimental operations supplied from bulk storage facilities represent high hazard operations
and principal investigators must consult PFS-FEC for guidance.

Restricting orifices, excess flow valves (available from AGA), mass flow controllers, or other
means must be used to limit flowing hydrogen to no more than 200% of the rate necessary to
support the experiments and operations in progress.

The concentration of hydrogen used in any operation must be the minimum concentration
necessary.

4.8.10 REQUIRED PRECAUTIONS

LINE SUPERVISORS MUST ENSURE THE PROVISIONS OF THIS SUBSECTION ARE

FOLLOWED.

Access to areas where hydrogen is stored or used must be restricted to qualified

persons.

Prior to hydrogen loading, all hydrogen systems must be leak tested with helium and
soap solution as close as practical to operating temperatures and pressures. Leak testing
must be repeated following system modifications and periodically as determined by the
experiment review.

All hydrogen systems must be purged with inert gas (typically helium, nitrogen, or argon)
prior to operation, and the purge process must be repeated when the experiment or operation is
shut down or restarted, or at other intervals determined by the responsible division. The purge
cycle must be a minimum of four system volume changes. A determination of the absence of an
oxidant (air or oxygen), water vapor, or hydrogen may be necessary to confirm the
effectiveness of a purge.

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 Page 7 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

Enclosures containing hydrogen cylinders, fittings, valves, regulators, etc., must be

vented to a safe location to minimize the accumulation of hydrogen.

Continuous hydrogen detectors, when provided, must be calibrated, installed,

maintained, and tested in accordance with the manufacturers recommendations. The need
for such detection must be determined by the safety review. Due to hydrogens potential to act
as an asphyxiant, line supervisors may need to consult an industrial hygienist regarding
whether or not such detectors are necessary. It should be understood that detectors sample
hydrogen concentrations at the detector location, not at the point of hydrogen release.
Consequently, they do not necessarily provide positive warning of a potentially explosive
condition. Detector set points must be established on a case-by-case basis consistent with
minimizing detection time without incurring nuisance alarms. Where hydrogen detectors are
provided for unattended operations, they must be monitored by the building fire alarm system.

4.8.11 COMPONENTS AND EQUIPMENT

Line supervisors must ensure the provisions of this subsection are followed.

Hydrogen equipment must be designed and approved for hydrogen service and installed
in accordance with the manufacturers recommendations. Hydrogen equipment includes
cylinders, containers, piping, tubing, manifolds, valves, regulating equipment, flashback
arrestors, and other accessories, including portable gas meters for detecting and measuring
hydrogen.

Hydrogen regulators, hose, or other appliances must not be interchanged with similar
equipment intended for use with other gases.

Flashback arrestors must be provided on all hydrogen supplies and must be located
immediately downstream of the first regulator or other location determined by the safety review.
The flashback arrestors required by this section must be designed specifically for hydrogen
applications and used in accordance with the manufacturer's flow and pressure limitations.
Flashback arrestors designed for hydrocarbon flames may not stop hydrogen flames, and
flashback arrestors that are effective for a nondetonatable hydrogen-air mixture may not be
effective for nonair mixtures.

Because flashback arrestors are not effective on detonatable mixtures, experiments or

operations involving detonatable mixtures (typically fuel/air or fuel/oxygen mixtures) must be
specifically approved by the responsible division.

Table 4.8-1 lists materials recommended for gaseous hydrogen systems.

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 Page 8 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

Table 4.8-1 Recommended Materials for Hydrogen Systems

Component Gaseous Hydrogen Service
Gaskets Mylar(r), annealed copper, Teflon
Hoses High Pressure
Rupture disc assembly Forged steel flanges
Piping Uncoated wrought steel or any 300-series stainless steel
Tapes Teflon
Regulator diaphragms Stainless steel
Lubricant for O-rings Dupont Krytox 240AC; Fluoramics OXY-8; Dow Corning
FS-3452; Dow Corning DC-33; Bray Oil Braycote 601;
General Electric Versilube; Houghton Cosmolube 5100
From Table 6.1, NASA Lewis Safety Manual.

When determined to be necessary by the safety review, electrical equipment must

comply with NFPA 70, National Electrical Code (NEC), Article 501, as applicable.
Generally speaking, compliance with NEC 501 means that where there is an
unacceptable risk that an explosive gas concentration may occur

All electrical equipment must be explosion proof, positively purged, or intrinsically safe;

All exhaust fans must be nonsparking type; and,

Hot surfaces/components must not be exposed to explosive fuel gas/air mixtures. Hot
surfaces commonly encountered in laboratory situations include heating elements,
drying ovens, heating elements in thermostatic controls, diffusion pump heaters, hot
plates, light bulbs, and some electronic system parts. In many cases, it is more practical
to prevent an explosive atmosphere from developing than it is to eliminate all potential
ignition sources. Emphasis on confining leaks and providing adequate ventilation will
reduce the need for special electrical equipment. When in doubt, users should contact a
PFS-FEC fire protection engineer for assistance.

Due to the potential for inadvertent misdirection of flows or unintended mixtures, the use of
manifold systems for supplying hydrogen to multiple areas or experiments is not recommended.
Where manifold systems are used with flammable gases, they must be installed under the
supervision of personnel familiar with their proper design and installation.

Small diameter plastic tubing must be installed in hydrogen service only after consultation
with a PFS-FEC fire protection engineer. When installed, the tubing must be securely fastened,
properly supported, periodically inspected, and replaced when worn or damaged.

Pressure relief valves on hydrogen systems must be piped to an approved location, typically
to a laboratory exhaust.

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 Page 9 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

Portable gas meters for detecting and measuring hydrogen must be specifically
designed for this service. Use of inappropriate equipment increases the risk of fire or
explosion.

Laboratory equipment using low concentrations of hydrogen must be vented to the outside
of the building through proper ductwork, hoods, or a suitable burning system. Auxiliary air must
be added to ensure that any residual hydrogen is exhausted from the ductwork.

Pressure relief valves and pressure regulating devices must not be modified.

Analytical instruments (gas chromatograph, spectrometer, etc.) that use hydrogen as a

carrier gas must be installed and operated in accordance with the manufacturers instructions.

4.8.12 BULK STORAGE

Facilities storing bulk quantities of hydrogen (e.g., tube trailers) must be enclosed within a
fenced area and protected from vehicle traffic. Bulk storage facilities must comply with NFPA
50A, Standard for Gaseous Hydrogen Systems at Consumer Sites.

Gaseous hydrogen tube trailers must comply with Department of Transportation (DOT)
specification 3A, 3AA, 3AX, or 3AAX. The gas trailer installation must be designed in
accordance with the gas suppliers specifications.

Tubes or trailers must be located above ground and be accessible to delivery vehicles and
emergency response personnel. The facility must be separated from other occupancies in
accordance with OSHA regulation 29 CFR 1910.103, Tables H-1 and H-2. Where hydrogen is
stored outdoors, the area within 15 feet of any hydrogen container must be kept free of dry
vegetation and combustible material.

Hydrogen shutoff valves for bulk storage facilities must be clearly identified.

Line supervisors must ensure written instructions are posted at each bulk storage
facility. These instructions must identify where the supply truck is to be parked, how it is to be
secured prior to transferring hydrogen, the required qualifications for operators, transfer line
hookups, emergency procedures, and emergency telephone numbers.

Piping between the bulk storage facility and the building must be properly supported,
routed as directly as practical, tagged, grounded, and/or bonded. Buried piping must be
installed with certified, welded fittings, protected from physical damage (e.g., pressure-treated

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 Page 10 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

2x12s buried in the trench over the piping), and be arranged such that the integrity of the line
can be verified by pressure testing with helium.

4.8.13 POSTING AND BARRIERS

Line supervisors must ensure conspicuous warning signs are posted where hydrogen is
used or stored, stating "Hydrogen-Flammable Gas," followed by appropriate instructions such
as "no smoking," "no open flames," etc.

The means to shut down hydrogen supplies must be readily accessible and clearly labeled.

Hydrogen cylinders must be clearly labeled with an NFPA 704-compliant label indicating a fire
hazard classification of 4.

Hydrogen cylinders must be identified, stored, handled, and used according to the requirements
in ES&H Manual Section 13.2, Compressed Gas Cylinders.

4.8.14 OPERATING PROCEDURES

Line supervisors must ensure the preparation of, and must approve, written operating
instructions and procedures for all hydrogen experiments and operations, including start-up,
shutdown, normal and emergency operations, and purging. Unattended hydrogen experiments
or operations must be conducted only with specific approval of the responsible DD/DH.

4.8.15 EMERGENCIES

Dial 911 if an uncontrolled leak, fire, or other emergency occurs.

4.8.16 RELATED REQUIREMENTS

Compressed Gas Cylinders, Section 13.2

Experiment Safety Review, Section 21.2

Lightning Protection, Section 9.3

Personal Protective Equipment, Section 12.1

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 Page 11 of 11

Environment, Safety and Health Manual ANL-E

Chapter 4 HAZARDOUS MATERIALS
Section 4.8 Hydrogen Safety
Section last revised: July 1, 2003 Section last reviewed: July 1, 2003

4.8.17 REFERENCES

"BOCA National Building Code," Chapter 3, Building Officials and Code Administrators
International, Inc., 1996.

"Carriage by Public Highway," Code of Federal Regulations, Department of Transportation, 49

CFR 100 to 177 Subpart B.

"Gaseous Hydrogen Systems at Consumer Sites," NFPA 50A, National Fire Protection
Association.

"Hydrogen," CGA G-5, Compressed Gas Association, Inc., Arlington, Va.

"Hydrogen," Code of Federal Regulations, 29 CFR 1910.103, OSHA General Industry

Standards.

"Hydrogen," Loss Prevention Data Sheet 7-9,1 Factory Mutual (FM) Engineering Corporation,
June 1984.

"Hydrogen Propellant," NASA Lewis Safety Manual, Chapter 6.

"Hydrogen Usage in the Laboratory," Data Sheet 1-700-82, National Safety Council, Chicago,
Illinois.

"National Electric Code," NFPA 70, National Fire Protection Association.

Othmer, Kirk, "Encyclopedia of Chemical Technology," Volume 12, 3rd edition.

"Pressure Piping," ANSI B31.1, American National Standards Institute, New York.

"A Recommended Practice for the Classification of Flammable Liquids, Gases, or Vapors and
of Hazardous (Classified) Locations for Electrical Installation in Chemical Process Areas,"
NFPA 497, National Fire Protection Association.

"Safe Mixture of Hydrogen with Helium, Argon or Nitrogen," memorandum from L. F. Coleman
to CMT personnel, May 31, 1989.

"Storage, Use, and Handling of Compressed and Liquefied Gases in Portable Containers,"
NFPA 55, National Fire Protection Association.

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