Professional Documents
Culture Documents
Handling of
Cryogenic Fluids
THE INTERNATIONAL CRYOGENICS MONOGRAPH SERIES
APPLIED SUPERCONDUCTIVITY,
METALLURGY, AND PHYSICS OF
TITANIUM ALLOYS. E. W. Collings
Volume 1: Fundamentals
Volume 2: Applications
CRYOCOOLERS. G. Walker
Part 1: Fundamentals
Part 2: Applications
CRYOGENIC PROCESS ENGINEERING
Klaus D. Timmerhaus and Thomas M. Flynn
HEAT TRANSFER AT LOW
TEMPERATURE. W. Frost
HELIUM CRYOGENICS
Steven W. Van Sciver
MODERN GAS-BASED TEMPERATURE
AND PRESSURE MEASUREMENTS
Franco Pavese and Gianfranco Molinar
POL YMER PROPERTIES AT ROOM AND
CRYOGENIC TEMPERATURES. Gunther Hartwig
SAFETY IN THE HANDLING OF CRYOGENIC
FLUIDS. Frederick J. Edeskuty and Walter F. Stewart
ST ABILIZA TION OF SUPERCONDUCTING
MAGNETIC SYSTEMS. V. A. AI'tov,
V. B. Zenkevich, M. G. Kremlev, and V. V. Sychev
SUPERCONDUCTING ELECTRON-OPTIC
DEVICES. 1. Dietrich
SUPERCONDUCTING MATERIALS
E. M, Savitskii, V. V. Baron, Yu. V. Efimov,
M. 1. Bychkova, and L. F. Myzenkova
Safety in the
Handling of
Cryogenic Fluids
Frederick J. Edeskuty
and
Walter F. Stewart
Los Alamos National Laboratory (Retired)
Los Alamos, New Mexico
Edeskuty, F. J .
S a f e t y in t h e h a n d l i n g of cryogenic f l u i d s / F r e d e r i c k J .
Edeskuty, Walter F. S t e w a r t .
p. cm. (The i n t e r n a t i o n a l c r y o g e n i c s monograph s e r i e s )
Includes bibliographical references (p. - ) and index.
ISBN 978-1-4899-0309-9
1. Low t e m p e r a t u r e e n g i n e e r i n g S a f e t y measures. I. Stewart,
Walter F. I I . T i t l e . I I I . S e r i e s .
TP481.E34 1996
621.5'9*0289dc20 96-15817
CIP
10987654321
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise,
without written permission from the Publisher
To E. F. Hammel, Jr.
of the ever increasing costs of errors that lead to accidents, such errors can cause
the termination of what might have been a beneficial program.
The striving for safety in any field must be a continuing effort as long as new
production methods and new applications are developed. Since the writing of Safety
with Cryogenic Fluids, a great deal of research and development in cryogenic
technology has resulted in additional safety-related data and knowledge. Some of
this work has occurred because of accidents, and more of it has been done in time
to prevent accidents.
It is not our intention to replace or supplant the previous book. Rather, we
would like to add the benefit of our combined cryogenic engineering experience,
which now totals over 75 years, most of which has taken place since the writing of
Safety with Cryogenic Fluids. One of the later chapters in our book is devoted to
pointing out the necessity for continued research related to safety in the use of
cryogens. Hopefully, this book can take its place alongside Zabetakis's work when
the occasion arises that a subsequent book will further elucidate the issues to be
addressed in continuing safety research.
Because the present work is based on the experience of the authors, the subjects
contained herein are somewhat limited to our areas of experience. Other safety topics
are covered adequately in the Zabetakis book. Also, there is a constantly increasing safety
literature appearing in such publications as the proceedings of the biannual Cryogenic
Engineering Conference and International Cryogenic Engineering Conference. Safety is
always an important part of these conferences and other cryogenic symposia.
After an introductory chapter, Chapter 2 discusses the physiological hazards
accompanying the use of cryogens. Chapter 3 covers the phenomenon of embrit-
tlement of structural materials, and Chapter 4 contains a discussion of the stresses
that can occur because of the large temperature excursions, both static and transient,
that accompany work in the realm of cryogenics. Chapter 5 considers the potential
for pressure, buildup in a system containing a cryogen, and Chapter 6 covers the
potential hazard of condensation of higher boiling substances when subjected to
the colder temperatures of the cryogens. Chapters 7 and 8 deal with the hazards of
combustion of the combustible cryogens, namely, methane and hydrogen, and their
relevant properties. The great potential for increased use of these two substances
as cryogens makes this a topic that will assume ever greater importance, and
consequently a field for rapidly expanding work on their safety.
Chapter 9 gives a discussion of safety problems that arise in the handling of
liquid oxygen, and Chapter lOis devoted to the discussion of slush hydrogen, an
esoteric fluid that might find large-scale use in aerospace applications. Chapter 11
considers the existing guidelines, standards, rules, and regulations for the handling
of cryogenic fluids, and Chapter 12 outlines areas where future safety research work
is warranted. Chapter 13 presents a discussion of accidents about which the authors
have some knowledge, fortunately from the standpoint of being investigators rather
than perpetrators.
Preface ix
This book is written mainly in SI units, with the more common United States
Customary System units frequently included in parentheses for the convenience of
the reader.
Frederick J. Edeskuty
Walter F. Stewart
Los Alamos, New Mexico
Acknowledgments
The authors wish to acknowledge the patience and understanding of their wives,
Jeanette Bergren Edeskuty and Marleen Stewart. Without their constant encourage-
ment and understanding, the completion ofthis book would not have been possible.
We also wish to thank emergency room physician Dr. Celeste E. Puckett for
reviewing Chapter 2 and offering many helpful comments to improve its content.
xi
Contents
xiii
xiv Contents
Chapter 6 Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 73
6.1. Hazards Arising from Unwanted Condensation. . . . . . . .. 74
6.1.1. Condensation and Freezing ofInert Substances. . .. 74
6.1.2. Condensation of Substances F onning Combustible
Mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 75
6.1.3. External Condensation on Cold Surfaces. . . . . . . .. 76
6.2. Preventive Measures. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77
Introduction
Although there might be more than one safe way to design, build, and operate a
cryogenic system, the safety of any system depends not only upon the system itself,
but also upon its interaction with other systems. Therefore, a knowledge of accepted
safety practices and experience with existing systems is invaluable to safe operation
either in new or existing cryogenic systems.
In the case of cryogenic systems, safe operation is important for several
reasons. First, and by far the most important, is the necessity of avoiding injury
either to operating personnel or to the general public. This one reason must take
precedence over all other considerations.
Although of lesser importance, the financial losses that can accompany any
accident cannot be ignored. As a rule, cryogenic systems are expensive. For storage
vessels and transfer lines, it is almost always necessary to provide an insulation
system that usually means an additional enclosure (vacuum jacket). This amounts
to paying for two vessels where, with systems operating at ambient temperature,
only one would be required. Also adding to the expense is the sophisticated
technology involved in the interconnections and support systems that are needed
between the fluid container and the vacuum jacket as well as the additional
instrumentation that is frequently required. These factors combine to make cryo-
genic systems more costly.
A third reason for the emphasis on safety, which is ever increasing in impor-
tance, is the negative impact ofthe reaction, or possible overreaction, of the general
public to accidents. The public perception of the safety problems of working with
hydrogen has been referred to as the "Hindenburg syndrome" and has hindered the
development of systems that could safely use hydrogen as an ideal fuel. Another
example is the continuing public apprehension of liquefied natural gas (LNG),
which, at least in part, stems from the LNG storage vessel failure in Cleveland in
1944, in spite of the fact that the cause of that accident is well understood and such
accidents can now be prevented. That the power of public opinion is respected (or
even feared) can be seen in the medical application of nuclear magnetic resonance.
Because of the inordinate fear of the general public of anything containing the word
2 Chapter 1
In order to have a safe cryogenic process, the first requirement is to have a safe
system. This means that safety must be considered in every phase of the system
design, in its fabrication, in the system checkout, and throughout its operation.
Furthermore, it is not enough merely to have a safe system. It is also necessary that
the system be operated in a safe manner. In the past, accidents have been caused by
the extraordinary ingenuity exercised by operators in circumventing, frequently
with good intentions, the safety precautions that were built into a system.
In the design of a new system, safety must be considered from the first
conceptual design all the way through the design process until the final construction
drawings are made. Equipment selection must be made with knowledge of the
conditions to which the materials will be subjected, and appropriate choices of
materials must be made. The system as designed must be able to perform every step
of the intended operation in a safe manner as well as to be able to be stopped at any
point of the operation and come safely to rest. There must be sufficient instrumen-
tation to allow the operators to understand what is happening within the system. In
some cases there must be redundant or duplicate instruments to ensure the avail-
ability of the information needed to carry out safe operation Qr, if necessary, to shut
the system down safely.
At every step, safety advice must be available from safety experts. In all but
the smallest projects, design reviews are necessary, with the review committee
consisting of safety experts and cryogenic engineers as well as knowledgeable
people, who are not directly involved in the project. Initiation of construction must
await the full approval of the review team before proceeding. Safety must be
monitored during the construction phase to see that the fabricated system meets the
safety objectives that were established during the design or that resulted from the
design reviews. Design reviews are an important part of making sure that no safety
precautions have been overlooked. These reviews must have the objective of
determining and pointing out what untoward events might possibly happen that
could lead to injury or fatality or to loss of equipment. A safety analysis is frequently
required by the review committee. This should address the design features that have
been incorporated either to obviate any conceivable accident or at least to mitigate
its consequences. Accidents that must be considered include such possibilities as
pipe or vessel ruptures, inadvertent isolation of systems containing cryogenic
Introduction 3
fluids, portions of the system being struck by uncontrolled vehicles or other objects,
loss of insulating vacuum or other types of insulation failure, and acts of nature
such as earthquakes and floods.
During the system checkout, responsible parties must look for unexpected
behavior or lack of proper operation of any subsystem and be able to explain and
eliminate, if necessary, any such behavior. Leak checking is an important part of
system checkout. Although bubble detection with various leak-detection fluids
might be satisfactory for some situations, in critical areas, such as a possible leak
into a vacuum insulation space, more exacting procedures, such as the use of a mass
spectrometer helium leak detector, will be necessary.
The same kind of attention to safety must continue through the operation of
the facility. Plant maintenance must be carried out with high-quality workmanship,
according to preapproved plans. Plant documentation and operating checklists must
be kept up to date. Frequently this will require the continuing oversight of a safety
committee, also consisting of safety experts, operating personnel, and knowledge-
able persons who are not directly involved with the work. The system must be
designed and operated in accordance with written standard operating procedures
(SOPs) which must address the specific operation and must be kept up to date. All
but the simplest operations must be carried out according to written checklists, and
the available checklists and procedures must be written not only for the expected
operations, but also contingency checklists must be written for every conceivable
deviation from expected operation. If at all possible, the situation of trying to react
to an emergency with on-the-spot decisions is to be avoided. When there is
computer control, automatic response can be incorporated into the system operation
software when feasible. Often, remote operation is advisable. In any case, personnel
access should be restricted to those actually needed in performing the operations.
Even ifall the above is done, the safe operation of the facility still requires the
additional safety factor of well-trained and knowledgeable operators. The operators
must be completely familiar with every phase of operation of all equipment within
the facility. In addition, safety training is also advisable for personnel who would
be responding to emergency situations such as fires or massive leakage from a
cryogenic system.
Pilatre de Rozier must have been very familiar with the combustibility of
hydrogen, considering his experience gained in his lecture demonstrations. On
several occasions, he had succeeded, without injury, in inhaling hydrogen and then
lighting the exhaled hydrogen at the end of a glass tube held in his mouth. When
he tried the more daring experiment of inhaling a mixture of hydrogen and air, the
ensuing explosion left him wondering if he had blown out his teeth.l Later he
decided to fly a balloon across the English Channel. When he decided to place a
hydrogen balloon on top of a Montgolfier balloon, it was pointed out that the
container of highly combustible hydrogen was just above the Montgolfier balloon
with its open flame, needed to heat the contained air. His experience told him that
4 Chapter 1
because of hydrogen's density being about 14 times less than that of air, if the
hydrogen were to leak, it would go up, away from the flame. He neglected to
consider the much stronger effect of convection currents in the atmosphere.
Consequently, as the balloon approached the French coast, a flash of flame was
observed, and Pilatre de Rozier fell to his death.2 This is an example of the fact that
one needs complete knowledge of all of the possible effects in a given system.
Training for the operator must begin with the general fundamentals of the
safety problems to be expected from cryogenic fluids. This should then be followed
by training that more specifically addresses the systems and processes to be
encountered in his or her work. Additional on-the-job training is desirable. How-
ever, training must not consist merely of one operator training the next, who, in
tum, passes the training to a third operator, and so on. By the time that several
successive operators have been trained, some important features of the safety
training will probably have been omitted, and accidents will become more and more
likely. In many cases it is a good idea to provide training for emergency personnel,
fire department personnel, and police, so that if any of these organizations is called
upon to answer an emergency, they can do so in the safest possible way, for the
safety of both the general public as well as themselves.
All SOPs, checklists, and safety rules must be in accordance with existing,
applicable safety codes and government regulations (see Chapter 11). Periodic
checks and safety inspections must be made to ascertain that there is strict adherence
to safety rules and procedures. Checklists and system drawings must be kept up to
date, and safety rules that are no longer applicable must be eliminated or updated
as necessary. Retaining rules that are not applicable tends to weaken the observance
of the necessary rules.
Finally, extra care must be taken in the modification of existing systems. A
modification to an existing system requires careful examination of its conse-
quences. What looks like a simple change can lead to accidents, and this has often
happened.
a Refs. 5-11.
b Notation: MW, molecular weight; T, temperature (K); p, density (kglm\ P, pressure (MPa); l!Jiv, heat ofvaporization
(kJ/kg); V, volume; VI, vaporization index (Ko cm3/J), based on an ambient temperature of3oo K (see Section 1.2).
Subscripts: NBP, normal boiling point (at 1 atm pressure); 1, liquid at NBP; 2, gas at NBP; 3, gas at 101.325 kPa
(1 atm) and 0 DC; c, at the critical point.
C Estimated as an ideal gas.
d Air is not a single-component substance. The values given are based upon liquid air (21 % 02) and the vapor in
equilibrium with it.
e C02 is a solid at the I-atm sublimation point; heat of sublimination is at 1 atm pressure.
encountered is smaller. Table 1.1 lists some of the physical properties that are of
concern to safety in the use of the more commonly encountered cryogens as well
as a few higher boiling fluids (refrigerants) that are included for comparison. The
ratios of the density of the liquid at its normal boiling point to the density of the
corresponding gas in equilibrium with that liquid and to the density of the same gas
at 0 C and standard atmospheric pressure indicate the expansion that can be
expected as the cryogens first evaporate and then warm up to approach ambient
temperature. The vaporization index, VI, for a given fluid is the ratio of the
6 Chapter 1
The low temperature and relatively high density of cryogens can cause safety
concerns. Hazards in the handling of these fluids can arise in several ways. The low
temperature can freeze living tissue, a phenomenon that has been referred to as
cryogenic "bums" or frostbite. Cryogenic temperatures can also affect structural
materials by causing embrittlement and can also induce unwanted stresses either
as a result of the unavoidable thermal contraction or even as a result of thermal
gradients within a structure. The cryogens have the ability to condense and solidify
substances, such as water vapor or carbon dioxide, that freeze at a higher tempera-
ture, and this can cause safety problems if the resulting solids can block safety relief
passages, or if they can cause erosion in places like valve seats. The great expansion
that can take place when a cryogen evaporates can cause substantial displacement
or dilution of the oxygen content of the local atmosphere. If the expansion is not
allowed, enormous pressures can build up. In the case of some cryogens, their
capability to participate in chemical reactions, such as combustion, or their toxic
nature can result in additional hazards. These hazards can be categorized as
physiological, physical, or chemical.
Introduction 7
REFERENCES
1. Friend, J. N. (1951). Man and the Chemical Elements, Charles Griffin & Company Ltd., London.
2. Sweaton, W. A. (1955). Jean-Fran~ois Pilatre de Rozier, the first astronaut, Ann. Sci. 11(4),349.
3. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research Inc., Boulder, Colorado.
4. Bell, J. H., Jr. (1963). Cryogenic Engineering, Prentice-Hall, Englewood Cliffs, New Jersey.
5. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
6. Mills, R. L., and Edeskuty, F. J. (1983). Cryogens and their properties, in Liquid Cryogens (K. D.
Williamson, Jr. and F. J. Edeskuty, eds.), Vol. II, Chap. I, pp. 1-14, CRC Press, Boca Raton, Florida.
7. Jenkins, A. C. (1961). Summary of physical properties, inA~on, Helium, and the Rare Gases (G.
A. Cook, ed.), Chapter X, Interscience Publishers, New York.
8. Gosman, A. L., McCarty, R. D., and Hust, J. G. (1969). Thermodynamic Properties of Argon from
the Triple Point to 300 K at Pressures to 1000 Atmospheres, NSRDS-NBS 27, U.S. Department
of Commerce, National Bureau of Standards, Boulder, Colorado.
9. Prydz, R., and Straty, G. C. (1973). The Thermodynamic Properties of Compressed Gaseous and
Liquid Fluorine, NBS Technical Note 392 (Revised), U.S. Department of Commerce, National
Bureau of Standards, Boulder, Colorado.
10. Liley, P. E. (1987). Thermodynamic properties of substances, in Mark's Standard Handbook/or
Mechanical Engineers (E. A. Avallone and T. Baumeister III, eds.), 9th Ed., Section 4.2,
McGraw-Hill, New York.
1I. Weast, R. C., ed. (1986). Handbook a/Chemistry and Physics 67th Ed., CRC Press, Boca Raton,
Florida, Section C.
Chapter 2
Physiological Hazards
There are several mechanisms by which contact of cryogenic fluids with a person
can present a physiological hazard. The most obvious of these mechanisms is that
the low temperature can cause freezing ofliving tissue. Also, in the case of cryogens
other than oxygen, the large expansion that occurs upon evaporation and warming
to ambient temperature can result in dilution of the oxygen in the surrounding
atmosphere to the point where it cannot support life. In the case of a few cryogens,
toxicity can also be a problem, but, fortunately, these are not frequently encountered.
The low temperature of cryogens can cause serious damage to living organ-
isms. The injury can be immediate in the case of direct contact with a cold fluid or
with equipment that has been cooled to cryogenic temperature. In addition, the more
gradual cooling that may be caused by being subjected to a very cold atmosphere
for an extended period of time can also cause physical harm by inducing hypother-
mia.
can result in tissue necrosis and, possibly, gangrene. I However, records of such
damage show that tissue injury as a result of cryogen spills is rare. 2
Although numerous lecturers have demonstrated that a very brief contact with
liquid nitrogen, for example, does not necessarily cause any harm to the skin, such
a practice is not recommended by anyone without a great deal of experience in the
handling of cryogenic fluids. It is true that for very brief periods (one or two
seconds) of gentle contact (no rapid flow) with small quantities, the liquid nitrogen
does not directly contact the tissue because of the large temperature difference
between the skin and the fluid. This temperature difference causes the formation of
a gas film, and heat transfer to the skin occurs in the film-boiling regime, where the
heat transfer is somewhat slower. However, in spite of this apparent protection,
prolonging the contact any longer than a second or two can be sufficient to produce
serious tissue freezing. If the fluid (either liquid or cold gas) is traveling with a
significant velocity, freezing can occur almost immediately. Another way in which
freezing can be almost instantaneous is by contact with uninsulated, cold metal or
other cold equipment. In this case, there is no formation of a gas film between the
cold metal surface and the skin, and the heat transfer is much more rapid.
2.1.2. Hypothermia
In a case where prolonged exposure to a very large spill could occur, lowering
of the body temperature is a serious possibility. Body temperature is a function of
the production of heat within the body and the heat loss from the body. Body heat
is produced by metabolism, muscle activity, and shivering. When the body is
incapable of producing heat at a rate equal to the rate of heat removal, hypothermia
results. At a body core temperature below 35C (95 OF), generalized organ
dysfunction and central nervous system, cardiac, and respiratory depression occur.
At a lowering of the body core temperature below 28 C (82 OF), ventricular
fibrillation becomes more likely? Thus, even a minor decrease in body core
temperature is serious, and the consequences become more drastic as the lowering
of the temperature progresses.
that material should not be used. Leather gloves are good, but when they are to be
used for handling oxygen, the tanning oils should be washed out with a suitable
solvent before use. Long trousers, without cuffs, should be worn outside the shoes,
again to avoid the possibility of pooling cold liquid. Open or porous shoes should
not be worn.
The hazard of tissue freezing must also be considered in system design in the
location of vents and equipment that could become cold. All system vents must be
oriented so that venting fluids, either liquid or cold gas, cannot impinge on any part
of the body of either a worker or anyone else nearby. All vent pipes or other
equipment that could be cooled to cryogenic temperatures must be externally
insulated in any location where they could be inadvertently touched.
The onset of hypothermia is a slower process than the potential damage that
could be caused by the direct freezing of tissue. For this reason, hypothermia is less
likely except in cases where the egress from a spill area is blocked or if a person
should be rendered unconscious or immobile by other consequences of an accident
resulting in a large cryogen spill. Therefore, where such an occurrence could be
possible, it is necessary to ensure that more than one escape route is available and
that no one is allowed to work without the presence of or surveillance by another
person who could assist if necessary.
well as follow-up attention because tissue necrosis can be progressive and infec-
tious complications can develop later.
If there has been a massive exposure so that the entire body temperature is
lowered, hypothermia is a possibility. The symptoms of mild hypothermia include
apathy, confusion, lethargy, fatigue, forgetfulness, incoordination, shivering,
slurred speech, withdrawal, and increased pulse and respiratory rates. With progres-
sively deepening hypothermia, the shivering stops, and the pulse rate, blood
pressure, and respiratory rate are decreased. 3 Rewarming can be by immersion in
a warm water bath; also, treatment for shock may be necessary. The patient should
be treated extremely gently, made as comfortable as possible, and immediately
transported to the nearest hospital emergency room. In all cases of cryogenic
exposure, medical attention should be obtained as soon as possible.
2.2. ASPHYXIATION
As seen from Table 1.1, a large expansion takes place upon the evaporation of
a cryogenic fluid. An additional expansion occurs upon the gas warming to ambient
temperature. There is some variation from one cryogen to the next in the actual
volume ratios to be expected; however, for rule-of-thumb estimates, a factor of 1000
is frequently used as the ratio of the volume of the gas formed at ambient
temperature and standard atmospheric pressure to the volume of the same mass of
cryogen as a liquid. Consequently, the spill of a large quantity of a cryogen in a
confined space can lead to an atmosphere that does not support life.
When working with a cryogenic liquid in a closed room, it is necessary to
determine the maximum quantity of liquid that could be released under any
circumstance and to estimate the maximum depletion of the oxygen in the room
that could occur as a consequence of that release. For example, the instantaneous
spill of a common-size Dewar of liquid nitrogen (160 liters) in a laboratory with
dimensions of 5 m by 7 m by 3 m high would produce sufficient ambient-tempera-
ture gas to completely replace the entire room atmosphere, thus rendering the local
atmosphere totally inert and incapable of supporting life. If the spill were to take
place slowly, it is possible that the evolved gas would thoroughly mix with the room
atmosphere, with the result that the equilibrium mixture would be expelled from
the room. This complete mixing would result in a lesser decrease in the room's
oxygen content. However, without additional ventilation, even in this case the
oxygen content would decrease to less than 8%, still creating a lethal atmosphere
(see Table 2.1). If the cryogen's release or spill rate can be predicted and complete
mixing could be assumed, a ventilation rate that would prevent the oxygen content
of the room's atmosphere from becoming dangerously low could be calculated.
However, if the ventilation rate is not sufficient to thoroughly mix the atmosphere
at all points in the room, pockets of lethal atmosphere can still exist. Calculations
of this kind can be used to set a limit on the quantity ofliquid nitrogen in a specific
Physiological Hazards 13
% Oxygen at
I atm total pressureb At-rest symptoms
15-19 Decreased ability to perform tasks; may induce early symptoms in persons
with heart, lung, or circulatory problems
12-15 Respiration deeper, pulse faster, poor coordination
10-12 Giddiness, poor judgment, lips slightly blue
8-10 Nausea, vomiting, unconsciousness, ashen face, fainting, mental failure
6-8 Death in 8 min; after 6 min 50% die and 50% recover with treatment, 100%
recover with treatment in 4-5 min.
4 Coma in 40 seconds, convulsions, respiration ceases, death
a Ref. 6.
b In this table and elsewhere in this book, unless indicated otherwise, gas concentration percentages and ppm values
are on a volume or mole basis.
laboratory space and also serve as a guide to determine the necessary safety
precautions that must be taken, such as limiting access of personnel, requiring
continuous oxygen monitoring, or providing external venting of the equipment.
Closed volumes, such as tanks, are obviously dangerous to enter, even if they
have not seen cryogenic service. These volumes should be entered only with
extreme caution. The entire procedure should be carefully planned in advance with
attention being given to ways to ensure that the atmosphere is breathable and that,
if necessary, rescue is possible without endangering additional people. The tank
must first be warmed to ambient temperature. Typical precautions that can then be
taken include the disconnecting of all attached pipelines and providing a continuous
supply offresh air forced into the tank with the input air on one end of the tank and
the exhaust at the other end (care must be taken to avoid dead ends where a
nonbreathable atmosphere could still exist). Analysis of the tank's atmosphere may
be necessary, and voice or visual communication with anyone inside the tank is
desirable. Also, the rescue procedure should be decided before tank entry. It must
be remembered that a filter respirator is of no value in protecting against asphyxi-
ation. The entire procedure should be discussed with and approved by knowledge-
able safety personnel. Following a written procedure is advisable.
Even outdoors, the vapors from most evaporated cryogens, which are still cold,
can linger in low spots and present a hazard. If there is any doubt about the oxygen
content of the atmosphere in an area near where a cryogenic fluid has been
evaporating, personnel should not be allowed to enter the area without self-con-
tained breathing apparatus unless a test with an oxygen analyzer shows that the
atmosphere is safe. It must also be remembered that the gas evolved is not
necessarily uniformly distributed around the area where a spill has occurred.
Diffusion and convection currents are powerful dispersing forces. However, in the
absence of convection currents caused either by wind (outdoors) or ventilation
14 Chapter 2
(indoors), buoyancy can be more powerful than diffusion, and the degree of oxygen
depletion can then vary from one place to another. The vapors of a cryogen at its
normal boiling point will be negatively buoyant and could be expected to accumu-
late near the floor level. However, for hydrogen and helium, if the vapors are
quickly warmed, or if ambient-temperature gas is vented into the enclosure, the
oxygen depletion could be more serious in the higher portions of the room.
In the case of sudden or acute asphyxia, such as would occur from inhaling a
gas with very little or no oxygen content, unconsciousness is almost immediate. In
this situation a person can fall in a few seconds and can die within a few minutes
if prompt treatment is not obtained. In one such situation, one man entered a tank
and dropped unconscious within just a few breaths. A second man then entered the
tank to rescue him and also dropped unconscious. Then there were two people to
rescue. Unfortunately, the rescue efforts were not in time to save the first man.
Gradual asphyxia can occur if the oxygen content of the atmosphere is
gradually or only partially reduced. Any reduction in the normal oxygen content of
the breathable atmosphere is undesirable, but the lower the oxygen concentration,
the more dangerous is the hazard. Table 2.1 describes some ofthe consequences of
subjecting a person to a reduction of oxygen in the atmosphere.
Another insidious aspect about anoxia is that the victim is frequently unaware
of any danger. In fact a feeling of euphoria can set in, during which a potential
victim would be unaware of any danger and make no attempt to rescue himself.
One of the authors (FJE) is personally aware of an incident that occurred during
physiological training in which several people were placed in a large tank in which
the atmospheric pressure was reduced to simulate a high altitude. The simulated
altitude was such that the oxygen partial pressure in the tank's atmosphere was less
than the sum of the carbon dioxide pressure plus the water vapor pressure in the
lungs. Thus, it was necessary to breathe through an oxygen mask. To demonstrate
the hazard of anoxia, one man was asked to remove his mask and then identify red
or black playing cards while the man at his side faced the cards, one by one. After
about 15 seconds, the first man started to make mistakes in the identification. After
about 25 seconds, he stopped paying any attention to the task at hand and was
content to sit there with a smile on his face. His mask was quickly replaced, and he
suffered no ill effects. However, had the mask not been replaced, he would have
been content to sit there and die.
Table 2.1 shows the seriousness of oxygen deficiency. Furthermore, the results
shown are for working at one standard atmosphere (sea level). At a higher elevation,
the total atmospheric pressure will be reduced, oxygen supply will be at a lower
total pressure, and the hazard of oxygen deficiency will become more serious. Also,
if the diluent gas is carbon dioxide (C02), concentrations of CO 2 as high as 9%
(reducing the oxygen content to 19%) can only be tolerated for a few minutes at
most. At this CO 2 concentration, the body cannot rid itself of the CO 2 produced in
normal respiration.?
Physiological Hazards 15
2.3. TOXICITY
Most of the commonly handled cryogenic fluids are not toxic. However, ozone
(0 3), carbon monoxide (CO), and fluorine (F 2) are highly toxic and must be treated
with caution.
Carbon dioxide is usually not considered a cryogen, nor is it truly toxic.
However, for completeness, it will be discussed briefly here because of its common
usage. As discussed in Section 2.2, CO2 in small amounts has no deleterious effects
on the human body. However, CO 2 is the product of respiration, and excess
quantities must be removed from the lungs as they are formed in the body and
delivered to the lungs by the blood circulation system. A prolonged exposure to a
concentration of? .6% CO2 can produce headaches, dizziness, and sweating, and at
a concentration 10% or higher, unconsciousness can occur in less than one minute.
Prolonged exposure to CO2 at this concentration can be fatal. Impairment in
performance has been noted in prolonged exposure at CO 2 percentages as low as
3%. The Occupational Safety and Health Administration (OSHA) has established
an upper permissible limit of 5000 ppm (or 0.5%) for CO 2 exposure in an 8-hour
day. A short-term exposure limit (no more than 10 minutes) of 30,000 ppm (3%)
has been recommended. 8 First aid for a person suffering from overexposure is to
remove the person from the CO2 atmosphere (making sure that the necessary safety
precautions have been made for the rescuer). Ifbreathing has ceased, then artificial
respiration should be applied. The patient should be kept warm, and immediate
medical attention should be sought.
Ozone, the most reactive form of oxygen, is blue in the liquid form. Besides
being extremely toxic, 0 3 also presents an explosive hazard (see Section 9.7).03
is produced continuously in the outer layers of the atmosphere by the action of solar
ultraviolet radiation on the oxygen in the air. The concentration of 0 3 varies, but at
sea level it can be present to the extent of about 0.05 ppm. 9 At a concentration of
0.015 ppm, it has a barely detectable odor, and in concentrations as low as 1 ppm,
0 3 is a strong irritantto the respiratory system and eyes. 10 For the exposure of human
beings, the maximum permissible 0 3 concentration is 0.1 ppm, and 50-60 ppm is
presumed to be immediately fatal. First aid for 0 3 exposure consists of removal
from exposure, and, for severe cases, oxygen should be administered, and medical
attention should be sought. II
Carbon monoxide presents a hazard by inhalation. Chemical asphyxia occurs
because CO has an affinity to combine with the hemoglobin in the blood that is 300
times as great as that of oxygen. 12 By combining with the hemoglobin, CO renders
the blood incapable of carrying the needed oxygen to body tissues. At a concentra-
tion of 600 ppm, toxic symptoms will occur after an exposure of about one hour.
At 1000-2000 ppm, slight heart palpitations can occur in about one half-hour, and
headache and nausea in about two hours. Inhalation of a concentration of 4000 ppm
(0.4%) can be fatal in less than one hour. 13 The maximum permissible exposure
16 Chapter 2
limit of a worker during an 8-hour day or a 40-hour work week is 35 ppm. A person
suffering from CO exposure should first be removed from the contaminated
atmosphere and kept warm (making sure that the rescuer is not jeopardized by doing
so). If the patient is unconscious, he/she should be placed on one side. If the patient
is breathing, oxygen should be administered. If the patient is not breathing, artificial
respiration should be given along with administering oxygen. In either case, prompt
medical attention should be obtained.
With fluorine there can be a hazard either from inhalation or from contact with
the skin. All organic materials are extremely reactive with fluorine. At as Iowa
concentration as 50 ppm, breathing can be impossible without respiratory equip-
ment, and at 100 ppm skin irritation occurs. Fluorine has a sharp, penetrating odor
that makes the inhalation of toxic quantities unlikely, unless the individual is
trapped in an exposed area. Fluorine odor can be detected at concentrations down
to about 0.14 ppm. Thus, the nose is an effective and reliable fluorine detector. 2 If
fluorine odor is detected, personnel should leave the area, moving cross wind until
clear of the contaminated area. An individual who has been exposed to a toxic
fluorine atmosphere should be removed from that area and immediately deluged
with water. Contaminated clothing should be removed. Water flushing should be
continued for 15 to 20 minutes. A fluorine bum should be treated as a combination
chemical and thermal bum, and prompt medical attention should be obtained. 2 The
time-weighted average exposure limit for an 8-hour day or a 40-hour week is 1 ppm.
The short-term exposure limit ( 15 minutes) is 2 ppm. 14
REFERENCES
1. Gonzalez, F., and Walton, R. L. (1991). Cold-induced tissue injuries, in The Clinical Practice of
Emergency Medicine (A. Harwood-Nuss, C. H. Linden, R. C. Luten, G. Sternbach, and A. B.
Wolfson, eds.), Chap. 199,1. B. Lippincott Co., Philadelphia, Pennsylvania.
2. Ordin, P. M. (1983). Safety, in Liquid Cryogens (K. D. Williamson, Jr. and F. J. Edeskuty, eds.),
Vol. I, Chap. I, pp. I-57, CRC Press, Boca Raton, Florida.
3. Klainer, P. (1991). Hypothermia, in The Clinical Practice ofEmergency Medicine (A. Harwood-
Nuss, C. H. Linden, R. C. Luten, G. Sternbach, and A. B. Wolfson, eds.), Chap. 200, J. B. Lippincott
Co., Philadelphia, Pennsylvania.
4. Meryman, H. T. (1957). Physiol. Rev. 37,233.
5. Washburn, B. (1962). N. Engl. J. Med. 266,974.
6. Compressed Gas Association (1992). Oxygen Deficient Atmospheres (Less than 19.5%), Com-
pressed Gas Association Bulletin CGA SB-2, Arlington, Virginia.
7. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
8. Compressed Gas Association (1984). Carbon Dioxide, Compressed Gas Association Bulletin CGA
G-6, Arlington, Virginia.
9. Kaye, S. M. (1978). Encyclopedia ofExplosives and Related Items, PATR2700, Vol. 8, U.S. Army
Armament Research and Development Command, Dover, New Jersey.
10. Lewis, R. J., Sr. (1992). Sax sDangerous Properties ofIndustrial Materials, 8th Ed., Van Nostrand
Reinhold, New York.
Physiological Hazards 17
II. Gatwood, G. T., and Murphy, G. F. (1969). Safety in the chemical laboratory: Ozone hazards, J.
Chern. Educ. 46(2), AI03.
12. Compressed Gas Association (1989). Safe Handling of Liquid Carbon Monoxide, Compressed
Gas Association Bulletin CGA-P-13, Arlington, Virginia.
13. Schmauch, G. (1972). Liquid carbon monoxide: Market grows, Cryogenics and Industrial Gases
1972 (July/August), 19.
14. American Conference ofIndustrial Hygienists (1992). 1992-1993 Threshold Limit Values for
Chemical Substances and Physical Agents and Biological Exposure Indices, American Conference
of Governmental Industrial Hygienists, Cincinnati, Ohio.
Chapter 3
Embrittlement of Materials
temperature (about 110 K). The tank ruptured, spilling its contents. Because there
was not sufficient diking or channeling to control the spread of the spilled LNG,
approximately 4165 m 3 (147,000 ft3) of LNG spread rapidly over a wide area. There
were ignition sources within the spill area, and the subsequent fire damaged the
support system of an adjacent LNG spherical storage tank with a capacity of
2350 m 3 (83,000 ft3) so that it also spilled its contents. The spilled LNG entered
the sewer system and exploded there. The external flame reached a height of850 m
(2800 ft), and damage occurred up to 400 m (~mile) away. The death toll was 128,
and over 200 injuries were reported. Property damage was estimated at $6,800,000.
This accident set the LNG industry back several decades. 3
The strength of a structural material is usually determined by a test in which
a specimen (usually a round bar) is placed in tension. As the tension is increased,
the bar is stretched or strained. In the initial part of the test, the strain is proportional
to the stress, and if the stress is removed, the bar essentially returns to its original
dimensions. In this portion of the test, the specimen is referred to as being elastic.
If the material has some ductility, and ifthe applied stress is sufficiently great, there
is ,a departure from linearity, with the strain increasing more rapidly than is the case
for the initial linear relationship. At this point the bar will retain a permanent
elongation and will no longer return to its original length when the stress is released.
At some small, but arbitrary, amount of permanent deformation (frequently 0.2%),
the applied stress is defined as the yield stress. As the stress is further increased, the
elongation increases, and the permanent stretching of the bar also increases.
Rupture Rupture
I
I
I
I
I
I
I
I
-oj 10--0.2% Strain
Fig. 3.1. Typical stress-strain diagram for ductile and brittle materials,
Embrittlement of Materials 21
Eventually, a maximum stress is reached, and the bar begins to "neck down,"
causing an apparent decrease in the stress, and finally the specimen breaks. The
maximum stress is called the tensile or ultimate stress. A brittle material, on the
other hand, does not exhibit this yielding, and consequently no permanent defor-
mation is evidenced prior to rupture. Rather, upon reaching the ultimate strength,
the specimen abruptly breaks. This is a more hazardous behavior for a material in
use under stress. If operating stress in a ductile material should slightly exceed the
yield stress, the member can yield and relieve the stress while remaining intact. A
brittle material in the same circumstance can fracture without warning. Figure 3.1
illustrates the results of the tensile tests of ductile and brittle materials.
A test that is frequently applied to a material to determine its ductility is the
Charpy impact test. This test is performed on a notched bar with a rectangular cross
section. A weight on a pendulum is then allowed to strike the specimen and break
160
140
120
V
/
/
E
~1oo
i
~
CiS 80
//
1ic.. .f2\.
..
e:
III
or;
60
()
~r.
-
40
--
w--:-
-~
20
po--
/ 8?:
./ ..:z.-
o
o 50 100 150 200 250 300 350
Temperature (K)
Fig. 3.2. Charpy impact strength as a function of temperature for various materials. 4 (I) 9% nickel
steel, (2) 304 stainless steel, (3) Cl020 carbon steel, (4) beryllium-copper, (5) K-Monel, (6) titanium,
(7) 2024-T4 aluminum.
22 Chapter 3
it. The energy needed to break the specimen is a measure of the ductility of the
material. The results ofthis test, conducted over a range of temperatures extending
down to the lowest temperature of use, indicates the effect on ductility oflowering
the temperature. Figure 3.2 shows the effect of temperature on Charpy impact
values for several materials. From tensile tests, a measure of ductility can also be
obtained from the reduction in area at the location of the fracture, as well as from
the total elongation of the specimen. The rate at which the ductility decreases with
temperature, as shown by any of these parameters, is an important consideration
and can be used for guidance in material selection. Charpy impact values of
20.3 N'm (15 ftlb), or greater, have been considered acceptable. Unfortunately,
there is no direct way to relate the Charpy impact value, or these other indications
of ductility, to a safe operating stress for the material. 2 Thus, for accurate design of
cryogenic vessels, the more sophisticated techniques of fracture mechanics, applied
450
400 r\
350 ~
300 ~ ........
~ Tensile -
--
150
Yield
100
50
o
o 50 100 150 200 250 300
Temperature (I<)
Fig. 3.3. Yield and tensile stress of 5086 aluminum as a function oftemperature. 5
Embrittlement of Materials 23
to data taken on the material under consideration, should be used to determine safe
operating stresses.
Another insight into the ductile or brittle behavior of a material can be gained
from the examination of a plot, for a given material, of the tensile and yield strengths
as a function of temperature. In general, both of these strengths increase as
temperature is lowered. However, the rate of increase can lead to an understanding
ofthe change in ductility of the material being tested. Figure 3.3 shows the behavior
of 5086 aluminum, a material satisfactory for cryogenic service. The figure shows
that the tensile strength increases faster than does the yield strength as temperature
is lowered. The distance between the two curves is an indication of the ductility of the
material. As shown in Fig. 3.3, this distance increases as the temperature is lowered.
This type of behavior indicates that the material is becoming more ductile as the
temperature is lowered. Figure 3.4 shows the different behavior of AISI 430 stainless
steel. Here it is seen that the two curves approach each other at liquid-nitrogen
----
700
K
500
"""'" ~
~
"" --
"iU 4OO
a..
~
~
Ci5300
~eld
r----
200
100
o
o 50 100 150 200 250 300
Temperature (K)
Fig. 3.4. Yield and tensile stress of AISI 430 stainless steel as a function oftemperature. 5
24 Chapter 3
a Ref. 6.
b fcc and bcc refer, respectively, to face-centered cubic and body-centered cubic crystal structures.
temperature (77 K), and thus the material becomes more brittle as the temperature
is lowered. Hence, AISI 430 is not a satisfactory material for cryogenic service. 5
Metals that are used successfully at cryogenic temperatures include aluminum
and its alloys, copper and its alloys, nickel and some of its alloys, and austenitic
stainless steels. In general, these are all metals with a face-centered cubic (fcc)
crystal structure. However, unstabilized austenitic stainless steel (some of the 300
series) can revert to a martensitic structure when stressed above the yield stress at
low temperature. Presence of the martensite structure reduces the ductility of the
metal. Table 3.1 lists some metals that are suitable for cryogenic service, as well as
some that are not.
a Ref. 8.
with one or more of the constituents of the metal. An example would be the
combination of hydrogen with carbon to form methane gas or with oxygen to form
water vapor, which could then form blisters in the metal and weaken it. If the
reaction is with the base metal or any of its alloying elements, the resulting solid
hydrides are usually very brittle and also have a lower density than the parent metal.
Thus, additional stress is induced by the expansion of the hydride that was formed
and then confined within the metal. 9
Iron or aluminum can react with water to produce a metal oxide and liberate
hydrogen. Acid cleaning, electroplating, or other finishing operations are also
sources of hydrogen. Internal hydrogen embrittlement has been the cause of
structural failures in members that presumably have not experienced hydrogen in
their use. Industry has experienced hydrogen embrittlement problems in high-hard-
ness springs, bolts, lock washers, valve and compressor parts, and gauges, particu-
larly when the parts have been electroplated. Delayed failure has been observed in
aircraft landing gear struts containing hydrogen that was introduced during the
processing of the metal. In some cases, collapse occurred while the aircraft was at
rest on the ground after successfully withstanding several hard landings. 9
a Ref. 13.
Embrittlement of Materials 27
ment is more serious with bcc and hcp metals. Also, as a rule of thumb, a metal in a
high-strength condition is more susceptible to HE than the same metal in an annealed
condition. This effect is shown in Table 3.3, which reports the results of ultimate tensile
tests on several metals, in different strength conditions, tested after having been
subjected to either hydrogen or nitrogen pressure. For the 4140 steel the decrease in
tensile strength was about 15% in the low-strength condition, whereas in the
high-strength condition the strength decreased by about a factor of3. 13
Although HE has been observed over a somewhat wider range of temperature,
for many metals and alloys the effect of internal and environmental HE maximizes
between -100C and + 100 C.12 Thus, both internal and environmental HE show
the greatest effect around room temperature (200-300 K). Measurements of plastic
strain illustrate this behavior (see Fig. 3.5), showing that the effect of HE decreases
1.0+-------.r-1--~==::::+_~----+_-____::;;;.:..::....__1
0.8+-----+---\-~--l~---_d.........,,:::::::::::===-_l
:8111
~ 0.6+------+------1r----t-------+-+------1
iiI
~
~
a:: 0.4+------+-------'\----t--------.4--------1
0.2-t------+---------'t.:------:~----1-----__I
O.O+---.....----+----.---+----,.---+---,------l
o 100 200 300 400
Temperature (K)
Fig. 3.5. Effect oftest temperature on susceptibility to hydrogen embrittlement. 14 The plots of strain
ratio (hydrogen test/air test) vs. test temperature show ductility minima in three Fe-Cr-Ni alloys charged
with deuterium for three weeks at 69 MPa and 620 K.
28 Chapter 3
stresses and sharp notches. The embrittlement manifests itself in crack formation
requiring an incubation period. If the hydrogen can be removed before the initiation
of this crack formation, the effect of HE can be reversed. 9
The yielding ofthe metal can be an important factor in inducing the results of
HE. Walter and Chandler I 8 have shown that in the storage vessel materials that they
tested, the strength of unnotched specimens was not affected whereas the ductility
was greatly reduced. They also considered plastic strain an important factor that
can lead to premature failure by hydrogen embrittlement. 18 In the cases of pressure
vessels that have experienced failure, the failure has frequently been in the area of
welds where residual stresses could have been a factor, again pointing to plastic
strain as a factor in causing failure by HE.
Table 3.4. Metals and Alloys Embrittled by Hydrogena (Listed in Order of Decreasing
Susceptibility at Room Temperature)
a Ref. 9.
Embrittlement of Materials 31
REFERENCES
1. Rosenberg, H. M. (1971). The behavior of materials at low temperature, in Advanced Cryogenics
(C. A. Bailey, ed.), Chap. 3, Plenum Press, London.
2. Wigley, D. A., and Halford, P. (1971). Construction materials and fabrication techniques, in
Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 6, Academic Press, New York.
3. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
4. Durham, T. F., McClintock, R. M., and Reed, R. P. (1962). Cryogenic Materials Data Handbook,
Office of Technical Services, Washington, D.C.
5. McClintock, R. M., and Gibbons, H. P. (1960). Mechanical Properties of Structural Materials at
Low Temperatures, a Compilation from the Literature, National Bureau of Standards Monograph
13, U.S. Department of Commerce, Washington, D.C.
6. Timmerhaus, K. D., and Flynn, T. M. (1989). Cryogenic Process Engineering, Plenum Press, New
York.
7. Johnson, W. H. (1875). On some remarkable changes produced in iron and steel by the action of
hydrogen and acids, Proc. R. Soc. London 23, 168.
8. Gray, H. R. (1974). Testing for hydrogen enviromnent embrittlement: Experimental variables, in
Hydrogen Embrittlement Testing, ASTM STP-543, American Society for Testing and Materials,
Philadelphia, Pennsylvania.
9. Edeskuty, F. J., et al., (1979). Critical Review and Assessment of Enviromnental and Safety
Problems in Hydrogen Energy Systems, Los Alamos Scientific Laboratory Report LA-7820-PR,
Los Alamos, New Mexico.
10. Dodge, B. F. (1953). High pressure research in the chemical engineering department of Yale
University, Trans. ASME 75, 331.
II. Mills, R. L., and Edeskuty, F. J. (1956). Chem. Eng. Prog. 52(11),477.
12. Swisher, J. H., Keaton, S. C., West, A. J., and Jones, A. T. (1974). Survey of Hydrogen
Compatibility Problems in Energy Storage and Energy Transmission Systems, Sandia Laborato-
ries Energy Report SAND74-82 19, Albuquerque, New Mexico.
13. Cavett, R. H., and Van Ness, H. C. (1963). Embrittlement of steel by high pressure hydrogen gas,
Weld. Res. Supple. 1963 (July), 316s.
14. Caskey, G. R., Jr. (1983). Hydrogen Compatibility Handbook for Stainless Steels, E.!. du Pont de
Nemours & Co. Report DP-I643, Savannah River Laboratory, Aiken, South Carolina.
IS. Hirth, J. P. (1984). Theories of hydrogen induced cracking of steels, in Hydrogen Embrittlement
and Stress Corrosion Cracking (R. Gibala and R. F. Hehemann, eds.), American Society for Metals,
Metal Park, Ohio.
16. Birnbaum, H. K. (1990). Mechanisms of hydrogen-related fracture of metals, in Environment-
Induced Cracking ofMetals (R. P. Gangloffand M. B. Ives, eds.), NACE-l 0, National Association
ofCoITosion Engineers, Houston, Texas.
17. Oriani, R. A., Hirth, J. P., and Smialowski, M., eds. (1985). Hydrogen Degradation of Ferrous
Alloys, Noyes Publications, Park Ridge, New Jersey.
18. Walter, R. J., and Chandler, W. T. (1968). Effects of high pressure hydrogen on storage vessel
materials, Proceedings of the ASM Westec Conference, March 11-14, 1968, Los Angeles,
American Society of Metals, Metals Park, Ohio.
Chapter 4
Although there are exceptions over limited temperature ranges, materials generally
have positive thermal expansion coefficients. Usually, the temperature change from
ambient to cryogenic temperature will amount to as much as 200 K (360 OF) or
greater. This large temperature decrease will cause a significant thermal contraction
in any material being cooled from ambient temperature to cryogenic temperature.
However, the thermal expansion coefficient is also a function of temperature,
decreasing as the temperature is lowered. Figure 4.1 shows the temperature depend-
ence of the thermal expansion coefficient of copper.! Although there is still further
contraction below the temperature ofliquid nitrogen, usually over 90% ofthe total
contraction from room temperature to any lower temperature will have already
taken place at 77 K because of the decrease in the thermal expansion coefficient for
many materials with temperature. Consequently, in cooling from ambient tempera-
ture to any cryogenic temperature, there will be a thermal contraction of about 0.3%
in iron-based alloys, over 0.4% in aluminum, and well over I % in many plastics.
The first two of these figures give useful rule-of-thumb values for quick estimates.
The more accurate values needed for system design can be obtained from published
tables of integrated thermal contraction over the temperature range of interest.
Tables 4.1 and 4.2 give some representative examples? Figure 4.2 shows the total
integrated thermal contraction from ambient temperature down to any cryogenic
temperature for several materials. 3
The thermal contraction of the parts of a cryogenic system that will be cooled,
and thus will experience these typically large temperature changes, must be
considered in the design of the system. If the system design does not accommodate
this contraction, large thermal stresses can result. As an example, consider the
contraction of a 304 stainless steel rod or pipe, firmly fastened at each end and not
allowed to contract while it is being cooled from ambient temperature to the
33
34 Chapter 4
a Ref. 2.
b Thermal expansion = MILo x 105 (Lo = length at 0 K).
temperature ofliquid nitrogen (77 K). The elastic modulus, E, is defined as the ratio
of the stress, a, to the strain, E, of an elastic specimen:
E = alE or a=EE
where E will be in the same units as a (commonly psi) because E is the ratio of a
change in dimension to that dimension and is thus without units. E does not vary
greatly as the temperature is reduced into the cryogenic temperature range. Increases
are in the range of 5-20% as the temperature is lowered from 300 K to 0 K. For 304
stainless steel we can use an average value for E of 180,000 MPa (26.1 x 106 psi) and
an integrated thermal contraction of 0.3% (0.003). The resulting stress can be seen
to be about 540 MPa (78,000 psi). This is well above the allowable stress and,
depending upon the metallurgical condition, can be above the yield stress of 304
stainless steel. Such stresses are usually not tolerable and might result in broken
pipes, leakage of fluid, or damage to the pipe restraints. The allowable design stress
is listed for a number of materials in the ASME Pressure Vessel Code, Section VIII
(1983), and the values for some common construction materials4 are given in Table
4.3.
Thermal Contraction 35
1.8x1 0-5
1.6><10-5
L.-----
~
1.4x10-5
/
/
I
/
/
/
II
/
o
)
o 50 100 150 200 250 300
Temperature (I<)
It might be possible to use Invar piping without provision for its thermal
contraction because its thermal expansion coefficient is about one-sixth that of
stainless steel, and its elastic modulus is only about two-thirds that of stainless steel.
The resulting stress in this case should be well under the allowable stresses.
However, detailed design calculations must be made to determine that adjacent
parts of the system are not damaged by such an arrangement.
36 Chapter 4
2.0+---~~---+----+----1-----I~-----1
l1.5
~ Nylon
;a
~
C
.12
~
1:
8
11.0
CD
~
GI
CD
c::
::J
S
~
0.5
I minum
Fig. 4.2. Plots of linear thermal contraction of some common materials as a function of temperature,3
showing the total contraction at a given temperature as the temperature is lowered from 300 K to that
temperature. PTFE =Polytetrafluoroethylene.
Thermal Contraction 37
0 0 0 0 0 0 0 0 0
20 3 14 10 10 21 27 45 -1
40 11 38 39 37 65 82 115 -2
60 21 70 78 81 116 152 200 -1.5
80 34 109 126 142 173 235 300
100 49 154 181 217 235 329 410 4.5
120 67 205 242 301 301 432 525 8.5
140 88 261 310 393 372 542 650 13
160 110 321 385 493 444 658 785 17.5
180 134 385 467 600 531 778 940 22.5
200 159 452 556 716 618 900 1130 27.5
220 184 524 651 841 711 1024 1370 33
240 210 602 753 977 811 1152 1620 39
260 237 688 862 1124 921 1284 1875 44.5
280 264 782 980 1282 1045 1422 2130 50.5
300 291 889 1107 1450 1187 1566 2695 57
a Ref. 2.
b Thermal expansion = MiLo x 105 (Lo = length at 0 K).
C Abbreviations for materials: PE, polyester; FTH, fluorothene; PS, polystyrene; PTFE, polytetrafluoroethylene.
Allowable stress
Material [MPa (psi)]
Carbon steel (outer shell only)
SA-285 Grade C 94.8 (13,750)
SA-299 129.2 (18,750)
SA-442 Grade 55 94.8 (13,750)
SA-516 Grade 60 103.2 (15,000)
Low-alloy steel
SA-202 Grade B 146.5 (21,250)
SA-353B (9% Ni) 163.7 (23,750)
SA-203 Grade E 120.6 (17,500)
Stainless steel
SA-240 (304) 129.2 (18,750)
SA-240 (304L) 120.6 (17,500)
SA-240 (316) 129.2 (18,750)
Aluminum
SB-209 (1100-0) 16.2 (2,350)
SB-209 (3004-0) 37.9 (5,500)
SB-209 (5083-0) 68.9 (10,000)
SB-209 (6061-T4) 41.4 (6,000)
Copper
SB-11 46.2 (6,700)
SB-169 (annealed) 86.2 (12,500)
Nickel alloys (annealed)
SB-127 (Monel) 128.2 (18,600)
SB-168 137.9 (20,000)
a Ref. 4.
near-ambient temperature at the top (when the vessel contains a cryogen). The space
between the inner and outer shell must be sufficient so that the inner shell is free to
rise when the neck tube contracts or shortens. Also, if a gap occurs between the side
bumpers and the inner shell when the vessel is cooled to operating temperature, this
gap must be sufficiently small that any possible sideways motion of the inner shell
does not overstress the neck tube or its joints.
For many cryostats and for large storage and large transport vessels, the design
can be more complicated. Usually, internal piping must connect to the inner shell
and then exit the vacuum space in such a way as to provide continuous or
Thermal Contraction 39
overlapping vacuum insulation spaces from the Dewar to the transfer line. The
piping must have a sufficiently circuitous routing through the Dewar's vacuum
space to provide an effective thermal barrier to heat leak and to prevent overstress
in the piping, the inner shell, or the piping connections during thermal cycling of
the Dewar.
The insulation system is also an integral part of the Dewar design. Usually,
thermal stresses are not a problem in the smaller-sized Dewars that are convention-
ally used in laboratories (typically under one cubic meter in volume). Larger
Dewars (hundreds of cubic meters in volume) are usually fabricated with a carbon
steel outer shell (this shell remains at ambient temperature) and a stainless steel or
aluminum inner shell. Many of these vessels are field-fabricated, and the inner
surface of the outer shell and the outer surface of the inner shell cannot easily be
made to have a low emissivity. The radiation transport of heat from the ambient-
temperature outer shell to the inner shell at cryogenic temperature is an important
consideration in the design of a Dewar.
For small Dewars (a few liters), the radiation heat transport can be minimized
by silvering or polishing the above-mentioned surfaces to produce emissivities of
about 1-2%. For larger Dewars (and also newer smaller Dewars), the use of
multilayer insulation, consisting of numerous layers of reflective foils, serves the
same purpose. Either of these insulation methods requires a relatively high vacuum
(absolute pressure of 0.013 Pa or W-4 Torr or better) to decrease the in-leakage of
heat by convection or residual gas conduction.
For very large Dewars (tens to hundreds of cubic meters in volume), an
alternate insulation system involves the filling ofthe annular space between the two
shells with perlite powder. The powder serves two purposes: the reflective particles
decrease the radiation transport of heat, and the many tiny spaces between the
particles minimize the convection transport of heat so that the vacuum requirements
are much less demanding (1.3 Pa or 10-2 Torr). Also, the perlite powder is relatively
inexpensive. The evacuated-powder insulation method is mainly used in larger
vessels where it is easier to provide relatively thick insulation spaces, typically
about one meter in thickness.
A problem that has arisen with evacuated-perlite insulation systems is the
shifting of the powder upon thermal cycling of the Dewar. Upon the initial filling,
the powder is uniformly distributed in the annular space between the two shells.
When the inner shell is cooled to operating temperature, the thermal contraction
can produce a void under the inner shell. During the time that the Dewar contains
cryogenic liquid, this gap can be partially or completely filled as some ofthe perlite
falls down into the gap beneath the inner shell. When the Dewar eventually becomes
empty and is left to warm up to ambient temperature, either to be serviced or because
it is not necessary to keep it filled, the inner shell will expand to its original size,
and the excess perlite underneath the inner shell will not flow up to its former
position. Thus, an upward force can be imposed upon the inner shell and on its
40 Chapter 4
- . - Perlite
Fig. 4.3. Perlite compaction mechanism. 5 Perlite can fall into the gap caused by the thennal contraction
of the inner shell but cannot be squeezed out upon subsequent wanning. Thus, stress can build up.
support system. The same phenomenon can also occur at the ends of horizontal,
cylindrical vessels. Ifthe Dewar is unsymmetrically supported, longitudinal forces
can also develop. This phenomenon has been called "perlite compaction." Figure
4.3 illustrates the perlite compaction problem in the vertical plane. 5
The perlite compaction problem has several solutions. One solution is to apply,
to the outer surface of the inner shell, a soft, flexible bat (glass wool or rock wool)
that either can be squeezed or can expand to fill the gap. Then the perlite powder
is filled into the remaining annular space. Another solution is to design the support
rod system to accommodate the motion of the inner shell without building up any
stress. A way to do this would be to have the vertical support rods pass through a
horizontal pad welded to the outer surface of the inner shell so that the weight of
the inner shell rests on a nut on the underside of the pad. In this way the inner shell
will be free to rise if it experiences an upward force when expanding against the
perlite powder and can descend onto the pad again upon recooling. With either of
these solutions, the flexibility of the piping in the annulus must be sufficient to
accommodate the motion of the inner shell.
The inner-shell motion caused by perlite shifting has been known to break
support rods and crack the bellows between the inner and outer shell of a horizontal
cylindrical Dewar that contained a manway for entry to the Dewar's interior. The
crack then caused a leak from the manway into the annular space and destroyed the
operating vacuum. Figure 4.4 shows the way in which the problem arose in the
horizontal vessel. From Fig. 4.4 it can be seen that the Dewar had one fixed support
and one sliding support to accommodate the longitudinal contraction and expansion
that occurs during temperature cycling. Because the internal piping was to exit the
inner shell on the end of the Dewar closest to the fixed support, it was necessary to
have a thicker insulation space on this end. On the other end, where the contraction
of the inner shell is the greater, the insulation space was thinner. This caused the
buildup of unequal longitudinal stresses (the largest buildup of perlite occurring in
Thermal Contraction 41
Evacuated Vacuum
Perlite Jacket
Fig.4.4. Schematic of Dewar damage by perlite compaction. Maximum contraction of the inner shell
occurs at the greater distance from the fixed support. In this case the same end also has the smaller
thickness of perlite. Perlite can fill in the end gaps formed upon cool-down. Upon subsequent warming,
because of the greater amount of perlite that was shifted and the smaller total thickness, the greater stress
will occur in the thinner perlite layer, causing a resultant force to the left.
the thinnest amount of perlite), with the result that the inner shell was forced toward
the end with the thickest layer of perlite. After a few temperature cycles the vacuum
deteriorated, and when the upper manhole cover was removed, the lower end of the
bellows was seen to have had its lower end, where it entered the inner shell,
displaced about 30 nun. Further inspection also revealed that support rods on the
fixed ends were broken off. In this case the solution to the problem was to place a
sliding cap, connected to the outer shell and fitting snugly over the end of the inner
shell nearest the sliding support. In this manner, the inner cylinder could contract
and slide within the cover, but the sliding cover could prevent the perlite powder
from entering the gap that would be formed upon cooling the inner shell. In
perlite-insulated cryogen-storage Dewars it is advisable to monitor the vacuum in
the insulation space periodically and also to look for unexpected frost spots.
without contact between the two concentric lines and without the buildup of any
undue stresses.
The contraction (shortening) of the inner line can be accommodated in one of
two ways. The first, and most commonly used, is the practice of designing the line
to have sufficient flexibility so that it can be distorted into a slightly different
position without causing a large stress. The flexibility is provided by including
elbows and "U" bends in the line. The alternative would be to use expansion bellows
in the line. Although possible, there are several disadvantages to the use of
expansion bellows in the inner tube of a transfer line. First, the bellows connections
are a possible source of future leakage, and if a leak were to occur, finding the leak
and repairing it would be considerably more difficult. Second, the motion allowed
by the expansion of the bellows is also a function of the pressure in the line. Thus,
to prevent unwanted contact between the two concentric lines, additional spacers
would be needed, with greater strength, and consequently more heat leak into the
cryogen space. Third, the expansion bellows constitutes a significant source of
pressure drop during fluid transfer.
The calculation for providing flexibility in a straight line with one "U" bend
has been described by Barron.4 Figure 4.5 shows a line with a "U" bend and gives
the definition of the line dimensions, W, H, and Lp ' so that the maximum stress,
Smax, can be calculated from Eq. (4.1). We can define a = W/Lp, ~ = H/Lp, and Et as
the integrated thermal contraction per unit length from ambient temperature to the
cryogenic temperature of interest (see Table 4.1). Then:
for a < ~, where E is the elastic modulus (Young's modulus), Do is the outside
diameter of the line, and
Each term in these equations is unitless. Hence, any consistent set of units can be
used.
For more complicated line routings, computer solutions are usually used, and
several versions are available, even for personal computers. The output usually
includes a diagram of the system indicating pipe locations and will show the
movement to be expected in cooling from ambient temperature to the final cryo-
genic condition. Stresses and moments are computed and can be tabulated for each
pipe section andjoint. The dotted line in Fig. 4.5 illustrates the final position of the
piping system after being cooled from ambient temperature to the operating,
cryogenic temperature.
r
Thermal Contraction 43
,-
_-' ,,\__ l
~~.~ ~I
Fig. 4.5. Original and defonned (after cooling to operating temperature) shapes of a "U" bend in a
cryogenic fluid transfer line.
The vacuum j acket must also comply with the motion of the inner line in such
a way as to prevent unwanted contact between the two concentric lines and undue
buildup of stress in that line. This is usually achieved by placing expansion bellows
on the outer line, which also accommodates ambient-temperature changes.
r- ,
300
290 V
LEGEND:
g280
V ,"
----Realistic Temperature ~ 270 / ,
Gradient ~ II ,
- - - - - - Linear Temperature i260
E250
/
,
Gradient
~24O /,
230
220
300
'i 250
~ 200
:z 150 .\
~ 100 \
iii 50 ,
~CD 0
I\,'
E -SO I'--. ' ,
,
~ -100
,
6 -150
80 100 120 140 160 180 200 220
Fig. 4.6. Dependence of stress upon the thermal gradient in a thick flange being cooled by flowing
liquid hydrogen. The dashed lines are for a linear thermal gradient, and the solid lines are for a more
realistic thermal gradient. The shaded area represents the flange; it has been opened up to insert the
graphs of temperature and stress.
Thermal Contraction 45
Aluminum, LN2
~
E 0.1 T--------''''''''~--t_""""~---------_I
The actual cool-down process, with its pressure and flow surges, is much more
chaotic than Fig. 4.8 suggests. However, the overall process does proceed as
described. During the cooling process, the local behavior as shown proceeds down
the line. Therefore, the exiting gas will remain relatively warm during most ofthe
cool-down process and will then rapidly decrease in temperature as the liquid front
approaches, just before liquid issues forth from the end ofthe line and the cool-down
is complete. (At locations in the line where thicker wall members, such as flanges,
are present, the cooling will be slower and some two-phase flow can persist.) The
concern during this process is with the two-phase portion shown in Fig. 4.8.
Two-phase flow can occur in a number of different ways (see Fig. 4.9). Most of
these flow types are not of concern. However, the occurrence of the stratified and
wave flow regimes can give rise to a situation in which, at a given cross section,
Thermal Contraction 47
FLOW .....
00
300
g
I-
20
Fig. 4.8. Cool-down model, representing the average behavior of a typical section of a long cryogenic
transfer line during the cool-down process. 8
~~~r-----~-~
PLUG STRATIFIED WAVE
~a-+--
_ ~
J.! - -
- ~I--~::::.~II:
~:-:!.1
SLUG ANNULAR DISPERSED
(almost aU liquid)
1111-BUBBLE
Fig. 4.9. Two-phase flow regimes. 9
48 Chapter 4
the bottom of the pipe (cooled by liquid) can cool faster than the top (cooled by
gas). If this were to occur to any great degree, the bottom of the pipe will try to
contract faster than the top, and the pipe will bow upward in the middle. This can
lead to unwanted stresses in the pipe as well as in its supports. 8
Baker9 has given a correlation that predicts the type of two-phase flow that
will occur under various conditions. The correlation is presented in Fig. 4.10. The
important parameters are the mass flow per unit area of liquid, L B, and of gas, GB
105 -r--------~--------~--------~_r------~------__,
Dispersed
Wave
Bubble or Froth
i ............ .. ..
Stratified
1~~-------+------~r-------r-------~~----~
Fig. 4.10. Baker's correlation,9 showing the type of two-phase flow to be expected under various
conditions. GB, gas mass flow rate [lbml(ft2.hr)]; LB, liquid mass flow rate [lbm/(ft2 hr)]; y, liquid surface
tension (dyne/cm); !iL, liquid viscosity (cp); pG, gas density (Ibmlft\ PL, liquid density (Ibmlft\ A =
[(pa/0.075)(prl62.3)]112; 'P = (73/Y)[(!iL(62.3/pd]1I2. The operating lines for the cooling process with
Dewar supply pressures of 103.4 kPa and 20.7 kPa show that raising the supply pressure results in faster
flow, consequently causing more of the cool-down process to occur before crossing into the stratified
or wave flow regimes.
Thermal Contraction 49
(defined in the caption to Fig. 4.10). The density of the gas and liquid phases and
the viscosity and surface tension of the liquid are the pertinent fluid properties. The
properties of the liquid and gas phases are compared to those of air and water, the
values for which are already contained in Baker's definitions of A and 'P. The Baker
plot is presented on a log-log basis; therefore, the entire evaporation process cannot
be represented on it. This is because the sum of LB plus GB must equal the total
mass flow, m. As the evaporation takes place, GB will vary from 0 initially to m
when all the liquid is evaporated, whereas LB will vary from m to O. Consequently,
the start and end of the evaporation process will always lie off the graph. However,
the process can be followed from, say, I % to 99% evaporation. If the corresponding
points for different degrees of evaporation are placed on the Baker plot, a prediction
of the type of two-phase flow at each point is possible. Note that increasing the flow
rate raises the locus of these points on the Baker plot, thus effectively moving more
of the vaporization process above the wave and stratified flow regimes. By
increasing the flow rate and consequently moving the locus of these points upward
on the Baker plot, most of the vaporization process can be made to take place in
one or more of the more favorable flow regimes. Although this method of analysis
has not been widely tested, the flows observed have fit the expected pattern in the
few cases in which it has been tested with liquid hydrogen and liquid nitrogen. In
one case with liquid nitrogen, where the flow was below the recommended
minimum flow rate, a one-ton vessel was lifted off the floor by the vacuum-jacketed
supply and return lines. These lines were 203 mm in inside diameter (nominal
8-inch schedule 40 stainless-steel pipe). To show conditions under which about
95% of the evaporation process can occur without entering the wave or stratified
flow regimes, calculations were made that give suggested minimum flow rates as
a function of pipe inside diameter for liquid oxygen, nitrogen, and hydrogen. to The
results are presented in Fig. 4.11.
The previous discussion presented reasons for not exceeding a maximum flow
and corresponding rate of cool-down of a cryogenic pipeline. For a long, horizontal
transfer line, it is also desirable to keep the cool-down flow above a lower limit to
avoid the bowing of the pipeline. It is possible that for a long horizontal line with
very thick flanges, these two flow rate limits would coalesce, or even overlap, thus
apparently precluding the cool-down of the line by flowing the cryogenic liquid
through it. If that case were ever to arise, the line could be cooled more slowly with
boil-off gas from the supply Dewar, thus eliminating the possibility of two-phase
flow in the line. Another possibility would be to introduce a smaller quantity of
liquid cryogen, stop the inflow, and allow the liquid to evaporate and repeat this
process over a long enough time so that only minimal temperature gradients would
exist at any time.
50 Chapter 4
100.-----------~----------_.----------_,r_--------~
50 LOX
10~----------1_------~~q_--~~----+_--------~
~
~
!
a:
1.0 -t-----;~~___l------_+_:"......=----_+-----___l
~
~ 0.5
0.1-t-~~--~--_+----------_+----------~----------~
0.05
0.01 +-..-----..--.--I---.--..-----..-+-~...___r_-.,......._+-_,_-,...___r_~
o 20 40 60 80
Pipe Inner Diameter (em)
Fig. 4.11. Minimum cool-down flow rate for nonstratified two-phase flow. 10
REFERENCES
I. Johnson, V. J., ed. (1960). A Compendium of the Properties of Materials at Low Temperature
(Phase I), WADD Technical Report 60-56, Part II, Properties of Solids, Office of Technical
Services, U.S. Department ofComroerce, Washington, D.C.
2. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research, Boulder, Colorado.
3. Wigley, D. A., and Halford, P. (1971). Materials of construction and techniques offabrication, in
Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 6, Academic Press, London.
4. Barron, R. F. (1985). Cryogenic Systems, Oxford University Press, New York.
5. Edeskuty, F. J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr., eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
6. Novak, J. K. (1970). Cool-down flow rate limits imposed by thermal stresses in liquid hydrogen
or nitrogen pipelines, in Advances in Cryogenic Engineering (K. D. Timroerhaus, 'ed.), Vol. 15,
pp. 346-353, Plenum Press, New York.
7. Dittus, F. W., and Boelter, L. M. K. (1930). University ofCalifornia Publications in Engineering,
Vol. 2, UCLA Press, Los Angeles, p. 443.
8. Bronson, J. C., Edeskuty, F. J., Fretwell, 1. H., Hammel, E. F., Keller, W. E., Meier, K. L., Schuch,
A. F., and Willis, W. L. (1960). Problems in cool-down of cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timroerhaus, ed.), Vol. 7, pp. 198-205, Plenum Press, New York.
9. Baker, O. (1954). Design of pipe lines for simultaneous flow of oil and gas, Oil Gas J. 53(July
26), 185.
10. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals
(G. G. Haselden, ed.), Chap. 11, Academic Press, London.
Chapter 5
From the large volumetric ratios shown in Table 1.1, one can infer that as confined
volumes of cryogens experience heat input, which they must unless there is a source
of refrigeration, pressure can build up. Unless gas can be vented from the system,
this pressure increase will continue until eventually either liquid density at ambient
temperature is approached or the container ruptures. Starting with saturated liquid
at 1 atm, the upper pressure limits that can be attained in this manner are enormous
and, in most cases, cannot be sustained without vessel rupture. Table 5.1 presents
estimates of these pressure limits, which can only be reached if, at the start of the
confinement, the container is completely filled with the liquid phase of the cryogen.
The pressures indicated in Table 5.1 cannot be reached before vessel rupture
in transport Dewars, nor in the usual laboratory experimental cryostats. Therefore,
it is necessary, in any cryogenic system, to provide safe and reliable relief systems
in every space in which liquid cryogen or cold gas could be trapped. This includes
piping systems in which fluid could be trapped in spaces such as between two valves
in series. There are two other volumes that must be protected against pressure
buildup. One of these is a volume containing a cold gas or cryogenic liquid that is
thermally connected to, and being cooled by, a volume containing a cryogen and
where pressure could build up when the external cryogen coolant is removed, either
intentionally or by normal evaporation. The other type of volume that must be
similarly protected is the evacuated insulation space of vessels or transfer lines
Maximum pressure
Cryogen [MPa (psi)]
Helium 103 (15,000)
Hydrogen 172 (25,000)
Nitrogen 296 (43,000)
53
54 Chapter 5
--
VENT _ _ _ _ _ _ _ _---,
containing a cryogen that is sufficiently cold to condense air. If such a space were
to have a very small leak, over a long period of time air could leak in and condense
on the cold surface of the inner vessel and exhibit essentially zero vapor pressure.
Thus, there would be no evidence of its presence. Upon removal of the cryogen,
the inner vessel will warm up, allowing the condensed air in the vacuum space to
exert its full pressure. Depending on the amount of air that had previously con-
densed, this pressure could be sufficient to rupture the vacuum j acket or to collapse
the inner vessel. For this reason the vacuum valve at the evacuation port of the
insulation space of a Dewar or cryostat is often built so that it can also provide
pressure relief if necessary. Figure 5.1 illustrates the three types of spaces that
require pressure relief systems. 1
Buildup of Pressure 55
Liquid density"
Cryogen Temperaturea (K) (gil) Vapor densitya (gil) Correction (%)
Heliwn 4.2 125 16.9 15.6
Hydrogen 20.3 70.8 1.34 1.9
Neon 27.1 1207 9.55 0.8
Nitrogen 77.3 808 4.62 0.6
Argon 87.3 1395 5.77 0.4
Oxygen 90.2 1140 4.47 0.4
In order to estimate the rate at which pressure will rise in a closed system
containing a cryogenic fluid, it is first necessary to know the rate of heat input into
the system. In the case of a Dewar, heat input is typically ascertained by measuring
the boil-off gas from the system while filled with the cryogen to be stored, once
thermal equilibrium has been established within the Dewar. For cryogens that boil
at higher temperatures, this is fairly satisfactory. However, for liquid helium, and
to a lesser extent liquid hydrogen, a correction must be applied to the value that
would be obtained by merely measuring the quantity of boil-off gas and using the
heat of vaporization to compute the heat input rate. This correction is necessary
because ofthe smaller relative difference between the density of the liquid and that
of the coexisting vapor at saturation temperature and pressure. As the liquid
evaporates, not all of the resulting vapor leaves the Dewar; some of it takes the
place of the liquid that has evaporated. For cryogens other than helium or hydrogen,
this correction amounts to less than 1%. For hydrogen and helium, the corrections
are 1.9% and 15.6%, respectively. Table 5.2 gives this correction for the most
common cryogens. For precise calculations of the heat input into a system using
the measurement of the boil-off gas quantity, these corrections should be applied
by increasing the heat input rate by the amount shown in the table.
Ifthermal equilibrium exists within the Dewar, and ifthe correct heat leak into
the Dewar is known, a calculation based upon the first law of thermodynamics can
then be used to provide an estimate of the rate at which the pressure will rise in an
unvented Dewar. The system volume and initial mass of cryogen (liquid plus vapor)
will be constant. With the known heat input rate, the total internal energy within
the closed system will be known as a function of time. These values can then be
used to compute the vapor and liquid fractions and the pressure of the system at
subsequent times. Details of the method to make such a calculation can be found
in a number of thermodynamics textbooks. 2
~
1.2,1--------,-------~--------r_------_r------_,r-------,_------_.
~
is 0.6 I II \
nan" I "\. .... k :::;::;>4.7':;::;=C I
w
Ul
~
a.
E
()
o 0.4 I "=1 ~.7 /1
0.2 I I -
0.0 I I I I 1 1 1
o 2 3 4 5 6 7 (")
Reduced Pressure, Pr ::r
=
~
..
Fig. 5.2. Generalized compressibility factor vs. reduced pressure for selected reduced temperatures. 3 Ul
Buildup of Pressure 57
At temperatures well above the critical point where only a single phase is
present, it is also possible to compute pressures by use of the gas laws. This might
be necessary if the individual gas properties are not available at the elevated
pressures that can be reached. However, it is of interest to note that for these very
high pressures, it is not possible to obtain accurate or even very close results with
the use of the ideal gas law, i.e.,
PV=nRT
where P is the pressure, V is the volume, T is the temperature, n is the number of
moles ofthe gas present, and R is the universal gas constant in units consistent with
the units used for pressure, volume, mass, and temperature. For fairly close
approximations, a modified formula can be used that is written as
PV=ZnRT
where Z is known as the compressibility factor and can be obtained from a chart
such as shown in Fig. 5.2, a generalized compressibility chart. 23 To use this chart,
it is necessary to use reduced pressures and temperatures to evaluate Z. The reduced
temperature, Tn is equal to the actual temperature (in units ofK or OR) divided by
the critical temperature of the gas (in the same units). Similarly, the reduced
pressure, P n is the actual (absolute) pressure divided by the critical pressure. Table
5.3 gives values of the critical constants for some of the more common cryogens.
To calculate a final pressure, it is frequently necessary to use an iterative procedure.
Unfortunately, with respect to limiting the rate of pressure rise in a Dewar,
thermal gradients are frequently encountered within cryogenic storage systems.
Figure 5.3 shows a horizontal cross section through either a spherical Dewar or a
horizontal, cylindrical Dewar. As shown, the heat will penetrate the insulation space
all around the circumference ofthe Dewar. The assumption of thermal equilibrium
implies that all of the liquid cryogen will be equally heated by the heat entering the
Dewar. When a Dewar has been venting against a constant discharge pressure for
a long time, the temperature will be fairly evenly distributed in the interior, except
for a small temperature gradient caused by the hydrostatic head in the fluid.
Fig. 5.3. Distribution of heat input into a cryogenic Dewar. Except for the heat entering the area at the
bottom of the Dewar, the heat that enters the storage volwne forms a warmer layer that can slide up the
inner wall and accumulate on the liquid surface.
However, when the vent is closed, then the temperature can start to stratify. Under
this circumstance, the heat that enters the sides of the Dewar first reaches the outer
layer of liquid, which, because of its slightly lower density, can slide up the inner
wall and collect on the liquid surface. The result ofthis process is that a warm layer
will slowly accumulate on the liquid surface and gradually grow in thickness. If the
Dewar is then allowed to vent at a higher temperature (and also a higher pressure),
given a long enough time, the warmer liquid layer will grow to fill the Dewar, and
thermal equilibrium will once more be approached. However, the pressure in the
Dewar will always be determined by the temperature ofthe liquid surface (its vapor
pressure). When the Dewar is closed off so that venting cannot occur, the heat
energy input into the Dewar is not equally distributed through all the liquid, and
the surface will have more than its share of the energy. Thus, the Dewar will
self-pressurize more quickly than would be the case were thermal equilibrium to
exist.
An example of this phenomenon was seen in the early 1950s during the
transport of liquid hydrogen in a 6_m3 (6000 L) trailer-mounted transport Dewar
from Boulder, Colorado, to Los Alamos, New Mexico. 4 This 644-km (400 mile)
trip involves a number of elevation changes, from an elevation of about 1630 m
(5350 ft) above sea level at Boulder to 1430 m (4700 ft) at Pueblo, Colorado, to
almost 3049 m (10,000 ft) over La Veta Pass to 1677 m (5500 ft) at Espanola, New
Mexico, to 2240 m (7350 ft) at the Los Alamos National Laboratory. During this
trip there was a concern that on one or more of the descents, the external atmos-
Buildup of Pressure 59
pheric pressure could rise fast enough that air could enter the Dewar and condense
to a solid with essentially zero vapor pressure, and the resulting mixture, which
could be dangerous, would give no evidence of its presence. Calculations made
with the use of the known heat leak into the Dewar showed that the Dewar could
be closed off for the 10-hour trip with a rise in pressure of only about 0.07 MPa
(10 psi). The 0.7-MPa (100 psi) pressure rating of the Dewar made it acceptable to
close off the Dewar at the start of the trip and then vent it back down to local
atmospheric pressure upon its arrival. This procedure was followed, and on the first
trip, after about two hours, the driver stopped for lunch. At that time the pressure
rise was seen to be about 0.014 MPa (2 psi), which was about what was expected.
During the time that the trailer was parked (approximately an hour), the pressure
rose about 0.07 MPa (10 psi). This was a cause for concern. However, the technical
courier realized that this inordinate pressure rise was probably caused by thermal
stratification within the Dewar and told the driver to start driving the truck. As soon
as the trailer was under way, the pressure then decreased to almost the same reading
that it had before the pause in the journey. The vibration of the stored fluid while
in motion was sufficient to thoroughly mix the fluid and bring it back to thermal
equilibrium. The remainder of the trip was uneventful.
Another example ofthe effects of thermal stratification was demonstrated with
an experiment performed at the Nuclear Rocket Development Station in Nevada
during the Rover Program (Nuclear Rocket Program). 5 In between two of the earlier
reactor tests, the vent systems were closed on two identica1200-m3 (50,000 gallon)
liquid-hydrogen storage Dewars. The boil-off had been measured previously and
shown to be the same for each of the Dewars. The results of this test are shown in
Fig. 5.4, from which it can be seen that the rate of pressure rise in one Dewar was
approximately three times that in the other. In Fig 5.4 the line with the lowest slope
is from a computation of the rate of pressure rise to be expected if thermal
equilibrium were present at all times within the Dewar. The line with the highest
pressure rise rate results from a calculation that assumed that all of the heat input
energy is deposited in a very thin layer at the top ofthe liquid (essentially all energy
goes into the ullage gas). Actually, neither of these limits could be attained, and an
intermediate behavior was expected. However, the variation by a factor of 3
between the two actual rates was unexpected. As required by the system design, the
two Dewars were connected to a common discharge line with one shutoff valve in
each Dewar discharge line and another shutoff valve in the common line down-
stream. This arrangement is discussed later in Chapter 7 and is shown in Fig. 7.2.
The volume contained between the three shutoff valves had been maintained filled
with helium gas at a pressure slightly higher than the maximum storage pressure in
the Dewars. The purpose of this procedure was to prevent leakage of liquid
hydrogen out ofthe storage Dewar in the event of a leak in the Dewar shutoff valve.
Examination, by gas analysis, of the gas in the ullage spaces of the Dewars showed
that helium gas had leaked into the Dewar that had the lower pressure rise rate. The
60 ChapterS
3~,-----------.-----------.----------,.---------~
Curve A, Calculated
(Energy Absorption by Ullage Only)
300+-----------~--~~--~----------+_--------~
Ii'
~2~1------------H~--------~-----------+--~------~
!
a.
~
~~ 200 1_-------I---~--------____"......- Curve B, Observed
from Dewar A
<0(
1~+-~--~L---+_------~~~=-------
Curve D, Calculated
(Uniform Energy Absorption, Uquid Only)
100~~~--~~~~--~T-~_+~--r-~~-+--~T-~~~
o 10 20 30 40
Time From Start (h)
Fig. 5.4. Pressure buildup from self-pressurization in two identical liquid-hydrogen storage Dewars. 5
helium leaking in was sufficient to stir the liquid hydrogen, keeping it closer to
thermal equilibrium throughout its volume. Thus, the helium gas leaking into this
Dewar resulted in a lower pressure rise rate than would have been the case if no
helium had been introduced.
Another experiment was performed on one of the above liquid-hydrogen
storage Dewars. 5 The Dewar was equipped with a vertical instrumentation rake
with a number of temperature-measuring elements to measure temperature as a
function ofliquid-hydrogen depth in the Dewar. Figure 5.5 shows the temperature
profile in the Dewar initially and then 38 h after the Dewar vents were closed. Here
it can be seen that, within the limits of sensitivity of the thermometers as shown on
the graph, the temperature of the bulk of the fluid did not change, and only on the
surface was there a noticeable increase in temperature. Also, it can be seen that the
E.
=
s:
C
't:S
So
."
til
~
c
til
20 40 60 80 100
Temperature (I<)
CI\
Fig. 5.5. Temperature profiles during self-pressurization in a liquid-hydrogen storage Dewar.5 -
62 Chapter 5
pressure rise over the 38-h period was about 0.l4 MPa (20 psi), and the surface
temperature during this time increased from 21.2 K to 24.2 K.
The data from Figs. 5.4 and 5.5 show that the pressure rise in a well-insulated,
large storage Dewar can be slow. However, it must be remembered that for such
Dewars the geometric configuration is favorable in terms of having the best possible
surface-to-volume ratio (spherical) and the insulation is good (I-m thickness of
evacuated perlite powder). Thus, the relative heat input is also low. Smaller systems
will experience faster pressure rises, and, of course, if the insulation should be
compromised (such as through a loss of insulating vacuum), the pressure can rise
much faster.
Another factor that must be borne in mind is that the lower the boiling
temperature of a cryogen, the greater is the temperature difference from ambient
temperature, or the driving force for heat introduction, and thus the greater is the
potential for a more rapid pressure rise. Table 1.1 lists the heats of vaporization on
a mass basis (kJ/kg) for common cryogens. For the consideration of pressure rise
in a vessel, it is also instructive to consider the heat of vaporization on a volume
basis (kJ/m 3 ). From the data in Table 1.1, one can calculate the heat of vaporization
per unit volume, showing it to decrease with decreasing normal boiling tempera-
ture. Thus, the same quantity of heat can evaporate more liquid as one progresses
to lower-boiling cryogens. At the same time, the temperature difference between
ambient temperature and cryogen storage temperature (the driving force for forcing
heat into the cryogenic system) is increasing. The vaporization index, VI, or
temperature difference divided by the volume heat of vaporization, is listed in the
last column in Table 1.1 and is a measure of the difficulty of storing and handling
a given cryogen as well as of its tendency to increase in pressure if confined.
The importance of maintaining the proper degree of vacuum in the insulation
space of either evacuated powder or evacuated multilayer insulation systems cannot
be overemphasized. Several publications in the cryogenic literature have given
correlations of the increase in effective thermal conductivity as the vacuum in an
evacuated thermal insulation system deteriorates. Over the range from the preferred
vacuum for evacuated perlite powder (about 1.3 Pa or 10-2 Torr) to 1 atm of air, the
effective thermal conductivity can be seen to increase by a factor of about 30. 6 For
multilayer thermal insulation the increase of pressure in the insulation space from
a maximum residual pressure of about 0.013 Pa (I 0--4 Torr) to 1 atm can cause a
corresponding increase of effective thermal conductivity of a factor of about 600. 6
Of course, the total heat input to the cryogen storage area is the sum of the heat
leaks through the insulation as well as from the support system and interconnecting
piping and instrumentation wires. For this reason the heat input into the Dewar will
not rise quite as rapidly as the above numbers might indicate. To estimate the
increase in the total rate of heat input would require a detailed knowledge of the
Dewar design. However, the effect of the increased thermal conductivity of the
Buildup of Pressure 63
thermal insulation will be by far the most important factor in causing either a much
higher evaporation rate or a much higher rate of pressure increase.
Because of the potential for increase in pressure, all cryogenic systems must
be protected against the trapping of cryogenic liquids, or even cold gases. Systems
should be equipped with duplicate, redundant venting systems. Often such an
arrangement consists of a relief valve in parallel with a rupture disk. In the design
of pressure relief systems, it should be remembered that the relief devices should
be sufficiently thermally spaced from the cold volumes so that they remain at
ambient temperature. The cooling of these devices can change the strength of the
bursting disk metal or the response to rising pressure of the relief valve and therefore
change the pressure at which they will relieve. Reliefvalves should be periodically
tested to see that they still operate as expected. Also, rupture disks should be
replaced periodically to prevent their becoming work-hardened by pressure vari-
ations within the volume being protected. It must be remembered that relief valves
may not reseat until warmed to room temperature.
Relief systems must be sized to be sufficiently large to accommodate the
maximum flow rate of either gas or liquid that could occur. The flow through the
relief valve or rupture disk must be adequate to be able to prevent the system
pressure from rising above its maximum allowable working pressure (MAWP). The
maximum boil-off rate of the stored cryogen should be calculated for the specific
cryogenic system being protected, and the relief valve sized accordingly.
Figure 5.6 shows a typical arrangement for the vent system for a large storage
Dewar. In this case two vent paths have been chosen, one for normal boil-offventing
and a second path for more rapid, operational venting when necessary. A separate
vent path should be provided for relief valve and rupture disk operation. A separate
relief path is also necessary for the evacuated insulation space. For cryogens that
boil at the higher end of the cryogenic range, the pressure relief on the evacuated
insulation space is necessary in case fluid leaks into it from the inner container. As
mentioned previously, liquid-hydrogen, liquid-helium, or liquid-neon storage De-
wars must also be protected against a leak from the external atmosphere. 1
In order to eliminate the possibility of air intrusion into the interior of a
cryogenic Dewar, it is usually a good idea to maintain the fluid storage space at a
pressure slightly above that of the local atmosphere. Even if the fluid container in
a cryogenic Dewar is to be operated at essentially atmospheric pressure, it still is
considered to be a pressure vessel because it is surrounded by a vacuum jacket.
Therefore, cryogen storage vessels must be designed and tested according the
ASME Pressure Vessel Code, Section VIII, for unfired pressure vessels. There may
be a problem with hydrostatic testing of a storage vessel that is designed for
64 ChapterS
A = m/RT/g)1)J12/KCPmax
where A is the flow area of the valve (m2), mj is the maximum mass flow rate from the
vessel (kgls),R is the universal gas constant [8314NmJ(kmolK) (1545 ftlbfflbmol OR)],
T is the absolute temperature of the gas at the inlet to the valve (K), gc is the unit
conversion factor in Newton's second law [1 kgmJ(Ns2) (SI units)], M is the
molecular weight of the gas (kg/kmol), K is the discharge coefficient (measured),
C is the expansion factor, and P max is the pressure at the inlet to the relief valve (Pa
= N/m2). The expansion factor, C, is determined by
C = {y[2/(y + 1)](y + J)/(y - I)} 112
Buildup of Pressure 65
where y is the ratio ofthe specific heats of the gas (Cpl Cv ),6,7 and Pmax is determined
by
P max = (Ll) [working gauge pressure (not MAWP)] + atmospheric pressure
Thermal expansion
Liquid coefficient (K- 1)
Waterb 0.0007
Oxygen 0.0044
Argon 0.0044
Nitrogen 0.0057
Neon 0.0144
Hydrogen 0.0164
Helium 0.210
pressure, usually two-phase flow will be encountered, and the rapid and large
change in volume between the liquid and gas can give rise to significant pressure
and flow oscillations. Temporary flow reversals can be encountered. Above the
critical pressure, these oscillations can still occur if the operation is near the
transposed critical line, where, even without vaporization, large volume changes
can occur over a small temperature range.
There are several mechanisms to produce oscillations, and the frequency of
these oscillations can vary from about 0.05 Hz to 10,000 Hz. In some cases the
pressure amplitude can be of the order of one-third of the system static pressure. 9
One mode of pressure oscillations was investigated by Bronson et al., 10 who
showed that the frequency of these oscillations occurring during the cool-down of
a long cryogenic transfer line could be analyzed by considering a spring-mass
system, a so-called Helmholtz oscillation. The gas in the warm, downstream portion
of the line was analogous to the spring, and the liquid in the upstream portion of
the line, where cooling was almost complete, could function as the mass suspended
on the spring. Experimental measurements of oscillations with a frequency of about
2 Hz in a I5-m-Iong (50-ft-Iong) transfer line being cooled with liquid hydrogen
showed good agreement with the theoretically derived relationship:
where fis frequency (Hz), y = Cp/Cv (ratio of specific heats), P is pressure (Pa),
LL is the length ofline already cooled and filled with liquid (m), Lg is the length of
line yet to be cooled and filled with gas (m), and p is the density of the liquid,
(kg/m3).
Thurston et al. II studied the conditions that produced Helmholtz oscillations
as well as acoustically driven oscillations, and Rogers 12 developed the following
empirical relationship with which they were able to predict the onset of these
oscillations:
Nboi = O.005/Nsv
where Nboi (the boiling number for incipient oscillations to persist) is defined as
Nboi = q/GMlv = (heat flux)/[(mass flux)(heat of vaporization)], with units of
(J/sm2)/[(kglsm2)(J/kg)] (thus Nboi is dimensionless), and Nsv is the dimensionless
specific volume number, given by(VG - VL)/VL , where VG is the volume of gas and
VL is the volume of liquid. If the actual boiling number, Nbo , is less than Nboi ,
oscillations will not persist, but if Nbo is greater than Nboj ' oscillations will persist.
Also, with the use of an amplitude number:
68 ChapterS
where p is the amplitude of the pressure variations,fis the frequency of the pressure
oscillations, D j is the pipe inside diameter, and G and llHvare as defined above,
they were able to correlate pressure amplitudes to within 40% by
Note that the boiling number, the specific volume number, and the amplitude
number are all dimensionless ratios and require the use of consistent units in their
evaluation. II
Guand Timmerhaus l3 have studied the conditions under which TAO can occur
in liquid hydrogen and liquid helium. One ofthe determining parameters is the ratio
of the temperature at the warm end of the tube to that at the cold end. The latter
temperature is not necessarily as cold as that ofthe liquid because ofthe possibility
of a thermal gradient in the ullage space above the liquid phase as well as from the
heat being conducted down the length of the tube along the thermal gradient that it
supports. The other parameters that determine whether an existing oscillation will
persist or die out are the temperature gradient along the tube, the diameter of the
tube, and the ratio of the length of the tube that approximates the warm temperature
to the length that approximates the cold temperature. These lengths would be easier
to determine ifthere were a discontinuous temperature gradient with all the change
in temperature taking place at a finite point along the tube. Although the gradient
may be steep at a point in the tube, it is not a step function. The shape of the
temperature gradient is also a factor in influencing the existence and frequency of
Buildup of Pressure 69
TAO. The closer the temperature gradient is to being linear, the less likely it is that
the oscillations will occur, but the higher is their frequency. Also, the closer to equal
the cold and warm lengths of the tube, the more likely it is that oscillations can
occur. For liquid helium, Gu and Timmerhaus found that tube diameters of about
1-2 mm are the most likely to allow the persistence of the oscillations. If the
diameter is smaller, the viscous drag will exert greater influence for damping, and
if the tube diameter is larger, the fluid inertia can exert a greater damping force. For
liquid helium they observed pressure oscillations with an amplitude in the vicinity
of 20 kPa (150 Torr).13 The figures in the paper by Gu and Timmerhaus allow an
estimate to be made of the conditions under which TAO will exist. For other fluids,
additional calculations must be made.
5.5. ROLLOVER
ignited under confined conditions. However, the hazard will be even greater if the
relief valves have not been sized to handle the greater than normal flow rate of the
boil-off vapors. Ifthey do not accommodate the increased flow rate at the maximum
pressure that the tank can stand, the pressure in the tank can rise sufficiently to
damage or even rupture the tank. The phenomenon of rollover has been known to
occur on a number of occasions. To the knowledge of the authors, no incident of
tank rupture has been caused by this phenomenon. Pressure relief valves have been
activated, but ignition of the evolved vapor has not occurred. IS Rollover presents
another mechanism by which there could be an abnormal pressure rise within a
cryogenic container; however, preventive measures that can be taken include
mixing of the stored fluid and decreasing the nitrogen content of the fluid.
tude. The degree of stabilization will determine the rate of normal-zone propagation
and also provide thermal capacity to limit the temperature rise.
With magnets cooled by immersion, pool boiling will occur. In the case of
magnets cooled by a forced flow of supercritical helium, the flow dynamics and
the convective heat-transfer coefficient will be strongly affected by the expanding
pressure pulse generated in the normal zone. The heating of the coolant fluid will
cause a corresponding pressure increase. In the case of large magnets, very high
pressures can be reached. For a 20-pancake coil with 12 turns/pancake, the total
coolant path length amounted to 446 m. If the full length of one pancake coil were
to quench, preliminary calculations indicate that a pressure in the vicinity of 43 MPa
could be reached even if the coil were vented. (Pressures on the order of 130 MPa
have been predicted in the case of an unvented pancake coil. 17) Thus, pressure relief
is required, and the pressure relief system must be sufficiently large to accommo-
date the venting of coolant needed to maintain a safe pressure within the magnet
enclosure.
The required vent rate will depend upon the magnet design, the rate of growth
of the normal zone,16 and consequent ohmic heating of the wire, and the rate at
which the heat transfer will allow this energy to enter the coolant.
The development of magnets utilizing high-temperature superconductors may
ease this problem somewhat because of the large increase in heat capacity of many
materials as the temperature is raised to the vicinity of75 K.
REFERENCES
1. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
2. Van Wy1en, G. J., and Sonntag, R. E. (1987). Fundamentals o/Classical Thermodynamics, 3rd
Ed., John Wiley & Sons, New York.
3. Dodge, B. F. (1944). Chemical Engineering Thermodynamics, McGraw-Hill, New York.
4. Laquer, H. L. personal communication.
5. Edeskuty, F. J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr., eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
6. Barron, R. F. (1985). Cryogenic Systems, 2nd Ed., Oxford University Press, New York.
7. Timmerhaus, K. D., and Flynn, T. M. (1989). Cryogenic Process Engineering, Plenum Press, New
York.
8. Sallet, D. W. (1978). On the sizing of pressure relief valves for pressure vessels which are used in
the transport of liquefied gases, Paper 78-WA/HY-39, presented at the ASME Winter Annual
Meeting, San Francisco, California, December 10-15, 1978, American Society of Mechanical
Engineers, New York.
9. Smith, R. V. (1971). Fluid dynamics, in Cryogenic Fundamentals (G. G. Haselden, ed.), Chap. 5,
Academic Press, London.
10. Bronson, J. C., Edeskuty, F. J., Fretwell, J. H., Hammel, E. F., Keller, W. E., Meier, K. L., Schuch,
A. F., and Willis, W. L. (1962). Problems in cool-down of cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 7, pp. 198-205, Plenum Press, New York.
72 ChapterS
II. Thurston, R. S., Rogers, J. D., and Skoglund, V. J. (1967). Pressure oscillations induced by forced
convection heating of dense hydrogen, in Advances in Cryogenic Engineering (K. D. Tirnmerhaus,
ed.), Vol. 12, pp. 438-451, Plenum Press, New York.
12. Rogers, 1. D. (1968). Oscillations in flowing and heated subcritical hydrogen, in Advances in
Cryogenic Engineering (K. D. Tirnmerhaus, ed.), Vol. 13, pp. 223--231, Plenum Press, New York.
13. Gu, Y., and Tirnmerhaus, K. D. (1994). Experimental verification of stability characteristics for
thermal acoustic oscillations in a liquid helium system, in Advances in Cryogenic Engineering (P.
Kittel, ed.), Vol. 39B, pp. 1733--1740, Plenum Press, New York.
14. Johnson, P. C. (1983). Liquefied natural gas, in Liquid Cryogens (K. D. Williamson, Jr., and F. J.
Edeskuty, eds.), Vol. II, Chap. 3, CRC Press, Boca Raton, Florida.
15. Sarsten, 1. A. (1972). LNG stratification and rollover, Pipeline Gas 1. 199(9), 37.
16. Wilson, M. N. (1983). Superconducting Magnets, Clarendon Press, Oxford.
17. Slack, D. S. (1989). Analysis of quench-vent pressures for present design ofITER TF Coils, Paper
presented at the 13th Symposium on Fusion Engineering, Knoxville, Tennessee, October 2-6,
1989.
Chapter 6
Condensation
All cryogens can present the hazard of unwanted condensation of substances that
boil at higher temperatures. Table 6.1 shows the estimated vapor pressures of some
of the substances that, ifpresent, can be condensed, usually to a solid, at cryogenic
temperatures. I From the magnitude of these vapor pressures it can be seen that, in
some cases, even undetectable amounts of substances can be condensed, although
probably only negligible quantities of solids could accumulate at such low concen-
trations. Table 6.1 indicates that any cryogen can almost totally condense water
vapor and carbon dioxide. Air can be condensed to a liquid at liquid-nitrogen
temperatures (possibly resulting in a condensate enriched in oxygen; see Section
6.1.2.). Argon, nitrogen, and oxygen are condensed to solids at the temperatures of
liquid neon, liquid hydrogen, or liquid helium. Finally, all substances, other than
helium, are solids at the temperature of liquid helium.
The ability ofliquid nitrogen to condense higher-boiling constituents affords
an inexpensive and very effective means to remove water vapor and carbon dioxide
to the extent that they exhibit essentially zero vapor pressure at 77 K. Frequent use
73
74 Chapter 6
nK Liquid
Fig. 6.1. Oxygen/nitrogen phase equilibrium diagram at 1 atm pressure. 5 Line A-B connects the
composition of condensing air to that of the condensate.
76 Chapter 6
Chapter 9). If the atmospheric air is condensed, the condensate, which is enriched
in oxygen, as mentioned above, can cause an explosive hazard if it is allowed to
fall upon a combustible surface such as an asphalt driveway. It is for this reason
that at liquid-hydrogen-unloading sites, the area under the storage Dewar, the
connecting piping, and the delivery trailer are always paved with concrete.
In the case of oxygen or air being condensed in liquid hydrogen, the exact
ignition mechanism may not be obvious, but combustion could be started by such
an occurrence as the rupture of a solid oxygen crystal by impact or by closing a
valve on the crystal. Also, in the case of fluid flow, the presence of solid crystals
can promote the accumulation of an electric charge on the particle. Therefore,
another possibility for ignition would be a spark caused by a buildup of electric
charge (see Chapter 12). In any case, the disposal of the liquid-solid mixture could
also present a hazard.
REFERENCES
I. Honig, R. E., and Hook, H. O. (1960). RCA Review 21,360.
2. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals
(G. G. Haselden, ed.), pp. 633--672, Academic Press, New York.
3. Croft, A. J. (1971). Cryogenic fluids, in Advanced Cryogenics (C. A. Bailey, ed.), Chap. 2, Plenum
Press, London.
4. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
5. Stewart, R. B., and Johnson, V. J. (1961). A Compendium of the Properties of Materials at Low
Temperatures (Phase II), WADD Technical Report 60-56, Part IV, United States Air Force,
Wright-Patterson Air Force Base, Dayton, Ohio.
Chapter 7
Combustion Hazards
One of the most feared hazards in any system is that of unwanted combustion. The
possibility of fIre and explosion is a legitimate cause for concern and for additional
attention to system safety. Although carbon monoxide, as well as oxygen and condensed
air (see Chapter 9), can present a combustion hazard, here we will be concerned with
liquid hydrogen and, to a lesser extent, with liquefIed natural gas (LNG).
mulation was noted in flowing gaseous hydrogen, although not sufficient to cause
an ignition in a hydrogen-air mixture. With liquid hydrogen, the charge accumu-
lation was even smaller.
The degree of electric charge that a flowing fluid can accumulate is determined by
its electrical conductivity. If the liquid has a conductivity of greater than W- IO 0- 1 cm- I ,
the charge that can arise from the ionization of the fluid can also dissipate. If, on
the other hand, the liquid has a conductivity less than 10-15 0- 1 cm- I , the buildup
of a charge is less likely. It is mainly with fluids that have conductivities between
these extremes that static charge accumulation is usually expected.
The electrical conductivity of liquid hydrogen has been measured5 and found
to be in the neighborhood of 10-19 0- 1 cm- I . Therefore, the accumulation of an
excessive electric charge might not be expected. However, if a charge does build
up, the very low conductivity ofthe liquid hydrogen will prevent rapid dissipation
of that charge.
There are ways in which a greater electric charge could build up within flowing
liquid hydrogen. Any type oftwo-phase flow could result in a charge accumulation
that could be very much larger. During the transfer of liquid hydrogen, two-phase
flow is commonly experienced, especially during the cool-down phase ofthe flow.
Another possibility is the presence of solid particles, either from solid impurities
that were not properly cleaned from the system or from higher-boiling gases that
have been condensed to a solid. The transfer of slush hydrogen is guaranteed to
involve solid particles, and the possibility of electric charge buildup should be
further investigated (see Chapters 10 and 12).
In the case of a solid particle entrained in flowing fluid, an electric charge can
be accumulated as it proceeds down the pipe. The energy accumulated equals
(CeV;)/2, where Ce is the capacitance of the particle and Ve is the accumulated
voltage. If a particle with an equivalent diameter of 1 mm accumulates a charge of
1.5 x 10---9 C (equivalent to 27 kV), it will have an electrical energy of 0.02 mJ. A
pressurized gas can sustain this magnitude of electrical stress, 6 and this energy is
sufficient to ignite a stoichiometric hydrogen-air mixture.
In the case of an unwanted ignition during gas flow, often it is not possible to
identify the ignition source. However, the total elimination of ignition sources from
static electricity and flowing particles is very difficult under field conditions. This
is another reason to strive for the highest possible level of cleanliness in cryogenic
systems.
venting the intrusion of air into the cryogen space. Although the release of a
combustible cryogen is necessary in the case of Dewar venting, either for depres-
surization, pressure relief, or normal boil-off, this type of venting will be done under
controlled conditions and will be discussed later (Section 7.2).
One way in which a combustible gas could be released is by a leak from the
system. This situation is more insidious because its onset cannot be predicted and
because the leak could occur in a number of different places. The leak does not
necessarily catch fire, but if it does, in the case of hydrogen, the resulting flame is
almost invisible in daylight. In the dark, a yellow-to-orange flame is usually visible.
In daylight it is possible to see heat patterns around the flame, but these are more
easily visible only if one is able to observe the area around the shadow of the vent
where the flame is erupting. In the case of a large leak that ignites, a concern is in
the possibility of personnel inadvertently entering the flame. Numerous sources
have suggested the technique of carrying a broom in front of the body so as to have
the burning of the more easily ignited bristles serve as an indicator of an unseen
flame. Another concern is the possible accumulation of a large mixture of combus-
tible gas with air in the range of combustibility, and the cloud then encountering an
ignition source.
The first line of defense against leaks is to have a leak-tight system that has
been carefully leak-tested under all operating conditions and maintained leak-free.
This includes both ambient-temperature and cold leak testing at operating pressure.
Second, combustible-gas-monitoring detectors with responding alarms should be
placed at appropriate points throughout the system. The obvious placement for a
leak detector is right above the point where the leak will develop. If there are some
places where a leak is more likely to develop, a detector should be placed there.
However, it is not always possible to predict where a leak could develop, and so
the question arises as to where the detectors should be placed. This is a strong
argument for the use of multiple detectors.
There are three mechanisms by which a leaking gas can spread throughout an
external volume. These are diffusion, buoyancy, and convection currents. Although
hydrogen has a high diffusion coefficient, diffusion velocity for hydrogen will be
in the neighborhood of a few centimeters per second. On the other hand, with
ambient-temperature hydrogen gas, buoyancy will cause upward velocities of a few
meters per second. As indicated in Chapter 1, convection currents are less predict-
able, can vary considerably, and can be much faster. Nevertheless, in the absence
of strong convection currents, the location of one of the combustible-gas detectors
should be above the apparatus being monitored. Where convection currents are
present, return air intakes are an additional location to be considered. This is another
reason that it is best not to rely on only one combustible-gas detector. 7
Combustion Hazards 83
Any system leakage that is detected must not be allowed to persist. Initially,
the system must be clean and leak-tight. The system must be fabricated with
materials that are not susceptible to cold embrittlement (or hydrogen embrittlement
in the case of hydrogen systems). Maintenance must be of high quality and well
documented. System instrumentation must include detection devices and alanns.
Overstresses must be avoided, and periodic retesting and recertification according
to ASME code is a good idea.
A common source of leaks in a previously tight system is through the seat of
a shutoff valve. For a gas system, the use of either a ring-and-blank flange or a
double-block-and-bleed system (shown in Fig. 7.1) is a good way to ensure that the
leaking of a shutoff valve does not allow the leakage to proceed into parts of the
system where it can cause damage. For a cryogenic fluid, neither of the above two
systems appears practical because of the requirement for vacuum j acketing in most
instances. For cryogenic service, the ring-and-blank flange would be difficult to
install and to operate. For the double-block-and-bleed system, a line that is open to
the atmosphere and is connected to the cold volume could present the hazard of air
condensation (see Chapter 6). For vacuum-jacketed systems, an alternative is
sometimes possible. Ifthere is a second valve downstream ofthe shutoff valve, the
volume contained between the two valves will be fitted with a relief valve (see
Chapter 5). As shown in Fig. 7.2, this section of line can usually be fitted with an
additional opening leading to a source of an inert gas (helium in the case of
liquid-hydrogen storage and nitrogen for LNG). The inert-gas pressure in this
volume can then be maintained at a pressure higher than that of the upstream
pressure during shutdown times. In this manner, ifthe shutoff valve should develop
=======~=======
the vent valve to the atmosphere closed. When
all three valve positions are reversed, any B
leakage through the upstream line valve will
be vented to the atmosphere rather than flow-
ing further downstream.
84 Chapter 7
Low Pressure
Regulated ---j)IcJ--t---t-I
Helium Supply
Sample_-DI<}-----'
Port
Fig. 7.2. Helium-block technique for a hydrogen shutoff system. 8 If one of the liquid-hydrogen shutoff
valves leaks, helium would leak into the Dewar, preventing liquid hydrogen from leaking out.
a small leak, the leak will be of the inert gas into the combustible cryogen storage
space, rather than of the out-leakage of the combustible fluid. 8
7.1.2.2. Purging
The previous discussion was concerned with the creation of unwanted com-
bustible mixtures that could result from an outflow or leakage of the combustible
cryogen from the cryogenic system. An equally important consideration, especially
in the case ofliquid-hydrogen storage, is the preclusion of the entry of air into the
cryogen storage volume. The first precaution is that of purging the air that remains
in the system after its fabrication or after it has been opened for any reason, such
as maintenance or modification.
Purging can be done by one of several methods, and the most effective method
should be chosen for a given system. F or systems that can be characterized as having
a short length-to-diameter ratio (a sphere would be the ultimate), the system can be
purged by evacuation and back-filled with an inert gas. If the evacuation is
sufficiently complete, the combustible gas can be directly admitted to the storage
volume. However, depending upon the process, either safety or operational con-
straints may require a more complete purge than merely one that reduces the air
Combustion Hazards 85
content below the flammable range. Any air remaining in the system after the purge
process is completed will condense to a solid upon contact with liquid hydrogen
and consequently present a hazard. Thus, it is possible that the purge process would
have to be repeated until a satisfactory condition is attained. As with all purging
operations, the degree of purge should be verified by gas analysis before proceed-
ing.
With some systems it might not be possible to ensure that leakage would not
occur when the system is at a pressure below that of the external atmosphere. Also,
some systems might not be able to withstand a total evacuation, although for most
vacuum-jacketed systems, this will not be the case. For such systems, an alternative
purging method is to pressurize the system with an inert noncondensable gas, allow
the gases to mix by diffusion (a slow process), and then vent the gas mixture. The
pressure that can be used will be limited by the system safe operating pressure, and
this method will obviously require repeated purge cycles until a satisfactory purity
level is attained.
For systems that can be characterized as having a large length-to-diameter ratio
(such as a pipeline), a flow-through purge with an inert gas is usually preferable. It
should be noted that merely flowing an amount of gas equal to the volume of the
pipe is not sufficient to effect a satisfactory purge. Several pipe volumes are
required.
In all purging operations, as mentioned above, the quality of the purge should
be verified by subsequent gas analysis. Furthermore, attention should be given to
dead-end locations. For either of the latter two methods of purging a dead-end
volume, it is possible to push the residual gas to the end of the pipe and then let it
merely expand back into its original volume. For the evacuation and back-fill
method, care must be taken that there is no leakage into the system during the time
the system is below ambient pressure. For some systems, a combination of purging
methods may be necessary.
Once the system is safely purged, the combustible cryogen can be admitted to
the system. After this is achieved, it is desirable to maintain the system at a pressure
above that of the surrounding atmosphere. This positive pressure should be suffi-
ciently great that a positive pressure with respect to the atmosphere will be
maintained through any variation of the external atmospheric pressure that could
occur. The difference in pressure should also be large enough that its presence is
readily ascertainable with the pressure monitors on the system. If the pressure of
the cryogenic system were to drop below the ambient pressure, the possibility
would exist for leakage of air into the system. This occurrence can be especially
hazardous in the case of the storage of liquid hydrogen, because the air will
condense within the storage Dewar to a solid, which will give no indication of its
presence. In this way, massive amounts of solid air could accumulate. Although it
would still require an ignition source to start any reaction, the resulting mixture can
be hazardous.
86 Chapter 7
In most cases there will not be any problem in maintaining a positive pressure
on the storage Dewar. However, this is not true for the storage of slush hydrogen.
One of the most pervasive safety problems in handling slush hydrogen is that its
vapor pressure is only about 7 kPa (52 Torr), and thus slush-hydrogen systems are
likely to be subatmospheric in pressure. Slush hydrogen is discussed later (Chapter
10).
In some instances, after the completion of an operation, post-run purging to
remove combustible gas from a system is required. This would be the case for some
maintenance operations or long periods of inactivity. As before, gas analysis is
required to determine the effectiveness of the purge. Also, it is necessary to ensure
that there is not enough leakage of air into the system during the initial part of the
post-run purge to create a combustible mixture within the enclosure at any time. In
addition, precautions must be taken to ensure that no residual combustible gas could
remain within the interstices of porous material or in dead ends of the system. The
post-run purge could start either with evacuation or with flushing of the system with
an inert gas before introduction of air. Again, the success of the purge must be
verified.
Another possible cause of an unwanted combustion can occur when starting
the evacuation of a system containing a combustible gas. If the vacuum pump is
initially filled with air and then the pump starts to evacuate a system filled with
hydrogen or methane (natural gas), the resulting mixture will pass through the
combustible range. An even greater hazard can result if the vacuum pump is
evacuating more than one system at the same time (not recommended). In that case
the mixture in the pump lines might always be in the combustible range. A similar
hazard could exist where the vent systems from more than one cryogenic storage
volume are interconnected. Explosions in vent systems have occurred, and in one
case an explosion occurred in a vent line carrying the boil-off from a liquid-hydro-
gen Dewar. In this case, more than one system was connected to a vent system that
was being flared (see Chapter 12). Fortunately, no serious damage was done, but it
was a reminder that it is a good idea to provide independent vents and evacuation
systems for every system carrying combustible fluids.
tg",,,,. r
high end of the flow range, up to 100 kg of hydrogen per second have been safely
vented and flared.
The flare stack is very effective and usually will burn almost all of the vented
gas. Flare stacks are used in a number of different applications such as LNG/lique-
fied petroleum gas (LPG) terminals, coal gasification plants, chemical plants, and
refineries. Each application is different and requires the appropriate flare stack to
meet the individual requirements. In addition to flow rate, gas combustion charac-
teristics, and temperature, the stack design must also consider prevention of air
entry into the volume of the stack, igniter design, the possible consequence of the
thermal radiation from the flame, and flame stability.9,]O The latter consideration
includes effluent velocity as well as wind direction and velocity. With improper
design, the flame might be able to lift off the top of the stack and in some cases
Combustion Hazards 89
Fig. 7.4. Hydrogen burn pond at Kennedy Space Center. Water has been drained for maintenance of
the plumbing.
even be extinguished, or the combustion volume could retreat into the stack or flash
back into it. Flare stacks are effective and safe if they are properly designed,
operated, and maintained.
Another method of flaring that has been used successfully is the burn pond
(see Fig. 7.4). In this case the hydrogen is piped under the surface of a water pond
to a header and then into a horizontal distribution system feeding vertical pipes
coming out of the water surface. Each of the vertical pipe outlets is capped with
a loose-fitting cap that just dips into the water surface and deflects the hydrogen
back to be released under the water to bubble up and bum just over the water
surface.
A precautionary note worth mentioning is that the aspiration of air into an
opening in the upstream portion of the vent system must be avoided. If this were
to occur, the air influx could give rise to a combustible mixture within the vent
system and cause a flash back into the system, which could either damage the
system or even result in a flame issuing from the opening. However, both of the
above types of flare system have been used successfully. They can operate over a
wide range of flow rates, and they can be turned off or on as required.
90 Chapter 7
80
60
g
-=c:
C>
Q)
....I
"0
:::l
B
.240
u
Q)
:c
'til
:::l
.D
E
8
20
D
Fig. 7.5. Combustible cloud length as a function of hydrogen release rate. 12 Curves A and B are for
nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and D are for daytime
releases with wind velocities of I and 3 mis, respectively.
Combustion Hazards 91
venting rates are only the few grams per second of normal Dewar venting, and
flaring is not required. During operational periods, the rates might be so high that
flaring of vented hydrogen is obviously necessary.
The possibility of a large unflared release ofliquid hydrogen or cold hydrogen
gas has received some study. 10, 11 The distance to which a combustible cloud can
extend depends upon the venting flow rate, the temperature of the venting gas, and
the local wind velocity and turbulence. Unfortunately, the presence ofa vapor cloud
does not necessarily indicate the limits of a combustible mixture. 10 Hydrogen gas
at one atmosphere and 20.3 K has a slightly negative buoyancy. Spill tests ofliquid
hydrogen have shown that most ofthe warming ofthe hydrogen is caused by mixing
ofthe hydrogen with the local atmosphere. 11 Once the plume becomes buoyant, the
rise rate and rise angle will be along the resultant vector of the buoyancy and wind
100
,
, ,
A,'
,
80 ,
,
, ,
~ ,
, ,
, ,
"C
;;;,
8 , ,
, "
,
~ 60
'iii ,
.B ,
,
E ,
8.5 ,
, , ,
, B, , ,
,,
-- -
,
~ 40 ,
::z: ,
5i ,
,
~
~
,
,
,
~
J:
, ,,
~
V
20
,
,
I
,
,
--
0
-
o --
, , '~
o 50 100 150 200
Hydrogen Release Rate (g/s)
Fig. 7.6. Mass of hydrogen in a combustible cloud as a function of hydrogen release rate. 12 Curves A
and B are for nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and Dare
for daytime releases with wind velocities of I and 3 mis, respectively.
92 Chapter 7
velocity vectors. Some calculations have been made to predict the length of a
combustible plume, the hydrogen inventory in the plume, and the height to which
the plume can rise. 12 (See Figs. 7.5-7.7.) It should be pointed out that these
calculations have been made for a release of hydrogen gas at a temperature of20 K,
and the only set of data against which they can be checked was taken for the release
of liquid hydrogen. This is an area where more safety analysis is needed (see
Chapter 12).
Atmospheric electric discharges, like lightning, can cause the gas from a
nonflared vent stack to ignite. It is not necessary for the lightning to strike the stack;
it need only strike within one or two kilometers. This phenomenon has been
10~----------~---------.----------.---------~
g
III
a:
E 6
:::J
.~
:;
'0
:::J
.2
(,)
Q)
jS 4
1ii
:::J
.0
E
8
2
Fig. 7.7. Maximum rise of a combustible cloud as a function of hydrogen release rate. 12 Curves A and
B are for nighttime releases with wind velocities of I and 3 mis, respectively. Curves C and D are for
daytime releases with wind velocities of 1 and 3 mis, respectively.
Combustion Hazards 93
Hydrogen/air fires do not present the hazard of toxic fumes and smoke that
other fires do. However, this will not be true if other combustible materials are
involved in the fire. This is one reason why good housekeeping practice does not
allow the presence of combustible materials in the vicinity of hydrogen systems.
As mentioned previously, the difficulty of seeing the flame can be an added hazard.
The occurrence of a fire causes changes in the surroundings that can be used
to detect the fire. These changes have been called the signature ofthe fire. Although
the nonluminous hydrogen flame makes visual detection difficult, there is a strong
heat effect and also turbulence of the surrounding atmosphere. Both of these
phenomena can be used in fire detection. 13 However, in a system in which there is
a large number ofplaces where leakage could occur, the fire detection system should
be capable of monitoring a large area over considerable distances.
The installation of a fire-water system in conjunction with liquid-hydrogen
storage has both advantages and disadvantages. Furthermore, there are two types
of water systems to consider: (1) a fixed spray over the tank and (2) a hydrant with
a hose.
The spray or deluge system is intended to protect the Dewar from external heat
sources (such as a fire in the fill or discharge connections). The purpose of the water
is to keep the Dewar cool to preclude a secondary safety problem that could arise
from an external fire overheating the Dewar's outer shell. The major concern is the
possibility of a buildup of pressure leading to rupture of the Dewar, causing a
boiling-liquid-expanding-vapor explosion (BLEVE). It should be remembered that
the Dewar is already protected against external heat by a vacuum jacket and the
intervening insulation. In any case, it is of utmost importance that water not be
94 Chapter 7
sprayed on the Dewar's vent system. If water were to impinge upon any part of the
vent system, flow paths could become blocked with ice, or relief devices could be
rendered inoperative, thus leaving the Dewar without a safe way to vent the normal
boil-off gas and allowing a dangerous buildup of pressure. If this were to occur, it
could be the cause of the very event that the water was supposed to prevent, a
BLEVE. In a few cases where large external heat fluxes from other sources have
been anticipated, fire-water spray systems have been installed. However, in many
cases this type of protection is not installed. There is a reluctance to allow water in
the vicinity of the Dewar because of the possibility of entry of the water into the
Dewar vent system with consequences as described above (see Section 13.2.1.3).
The second type of fire-water system would be a hydrant and hose installation
to offer cooling protection to equipment in the vicinity of the Dewar for use in the
case of a fire at the Dewar. The water requirement would be set by the nature of the
equipment to be protected. In general, gas storage cylinders, extraneous equipment,
and combustible materials should be kept away from liquid-hydrogen storage
Dewars. In the case of hydrogen being stored in a closed space special precautions
are recommended, including a limitation to the quantity of hydrogen stored, a
sprinkling system, and a pressure-relieving (blowout panel) area. In the case of a
hydrogen fire, the fire-water system must not be used to extinguish the fire. The
fire should be extinguished by shutting off the supply of hydrogen. To extinguish
the fire without stopping the supply of hydrogen will create the possibility of the
accumulation, and later ignition, of a larger combustible mass, with even more
disastrous consequences.
A decision to provide a fire-water cooling system would have to be made with
specific knowledge of the involved system. Although there may not be a universal
requirement for the provision of fire-water protection at a given location, it should
be remembered that local authorities, such as fire chiefs or facility safety officials,
have the authority to impose additional requirements and should always be kept
informed of the operations and emergency procedures that might be required. Their
input and cooperation should be sought. They should also be given any training
that they desire concerning the nature of the installation. Whenever possible, the
response to an emergency situation should be according to preplanned procedures.
Maximum overpressure
[kPa (psi)] Effect on personnel
7 (1) Knock personnel down
35 (5) Eardrum damage
100 (15) Lung damage
240 (35) Threshold for fatalities
345 (50) 50% fatalities
450 (65) 99% fatalities
Q Ref. 14.
Thermal radiation burns to personnel are a potential hazard from fIres involv-
ing combustible cryogens such as hydrogen or LNG. Human skin consists of two
main layers, the epidermis or outer layer, which is about 0.1 mm thick, and the
derma, a deeper layer 1 to 2 mm thick. 16 In a fIrst-degree burn, little or none of the
derma is destroyed. In a second-degree burn, all of the epidermis and a signifIcant
part of the derma are affected, and in a third-degree burn, all of the epidermis and
derma are destroyed. Experiments on pig skin, which closely resembles human skin
in its response to burns, have shown the effects of heat fluxes and duration of
exposure in causing burns.
Hardee and Lee l6 have correlated burn data to obtain the relationship between
the duration of the burn period and the amount of heat that must be absorbed by the
skin to produce second- and third-degree burns. These data are for a heat source at
a temperature in the vicinity of the combustion temperatures of hydrogen--air
(2318 K) and methane-air (2148 K) mixtures. 1 These data have been plotted in Fig.
7.8 to show the incident heat rate that can cause second- and third-degree burns as
a function of exposure time.
Two of the possible scenarios for a combustion are: (1) a release resulting in
a combustible cloud with delayed ignition forming a hemispherical or spherical
fIreball; and (2) a release with immediate ignition forming a flame approximating
a vertical inverted cone.
To compute the heat incident rate at a distance, Rfo from a combustion, it is
necessary to know the rate of energy radiated from the flame, and consequently, its
energy release rate, and the fraction of the combustion energy that is released as
radiation. This fraction has been given as 17-25% for hydrogen--air combustion
and 23-33% for methane-air flames. 1
At any given distance from the flame, the heat flux can be determined from
the total radiant energy evolution rate divided by the area of the surrounding sphere
at the distance under consideration. For a combustible cloud that has lifted off the
Combustion Hazards 97
10.-------------~------------~----------__;
ground, this can be approximated as a sphere, so at distance Rfi the area is equal to
41tR}. For a fireball, the burning duration can be approximated by dividing the cloud
dimension by the velocity of the flame (see Chapter 8). The rate at which radiant
heat is incident on a given area can then be estimated by dividing the total radiation
energy at distance Rf by the time of duration of the flame. For a continuous flame,
such as with a massive leak, the rate at which heat radiation reaches a subject can
be computed from the product of the rate ofleakage times the energy of combustion
times the fraction of combustion energy emitted as radiation divided by the above
area factor. The duration of the fire will be determined by the time that the leak is
allowed to persist.
For exposure to hydrogen flames of no more than 30-s duration, a distance of
55 m (180 ft) has been calculated to be sufficient to prevent second-degree burns
98 Chapter 7
d = 0.47(wi /3
where Wfis the mass of fuel in kilograms. A spill of 1.9 m 3 (500 gallons) of liquid
hydrogen was observed to bum for less than one minute. While this is not a precise
enough piece of data to serve as a check on the above equation, it must be
remembered that the flame time is also controlled by the evaporation rate. In any
case, hydrogen fires from a finite release are short-lived compared to fires due to
conventional fuels, and this fact has led to the conclusion that liquid hydrogen is a
safer fuel than conventional aircraft fuels in many instances. 19 This conclusion is
based upon the short burning time for heat transfer into the fuselage in a survivable
crash.
1x106~------------------------------~--------________-,
Experimental
i Areas
:i<Il 1x103
~
Qi
:::>
u..
Fire, Thermal Radiation
(Inhabited Buildings,
Undiked)
lx10i-------~~-.--~~L---~r_~----~~,_--~--~--~
1 10 100 1,000 10,000
Distance, RI (m)
Fig. 7.9. Quantity-distance relationships for the protection of personnel near liquid-hydrogen storage
and experimental areas (unbarricaded).l
REFERENCES
1. Hord, J. (1976). Is Hydrogen Safe?, National Bureau of Standards Technical Note 690, Institute
of Basic Standards, National Bureau of Standards, Boulder, Colorado.
2. National Fire Protection Association (1962). National Electric Code, Article 501-Class I
Locations, N:ational Fire Protection Association, Quincy, Massachusetts.
3. Cassutt, L., Biron, D., and Vonnegut, B. (1962). Electrostatic hazards associated with the transfer
and storage of liquid hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.),
Vol. 7, pp. 327-335, Plenum Press, New York.
4. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Contract AF 18(600}-1687, Arthur D. Little, Inc., Cambridge,
Massachusetts.
5. Willis, W. L. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
6. Willis, W. L. personal communication.
7. Chelton, D. B. (1964). Safety in the use ofliquid hydrogen, Chapter 10 in Technology and Uses
of Liquid Hydrogen (R. B. Scott, W. H. Denton, and C. M. Nicholls, eels.), Chap. 10, Pergamon
Press, Oxford.
8. Edeskuty, F. J. (1979). Safety, in Hydrogen: Its Technology and Implications (K. E. Cox and K.
D. Williamson, Jr., eds.), Vol. IV, Chap. 5, CRC Press, Boca Raton, Florida.
9. Straitz, J. F. III (1987). Flare technology safety, Chem. Eng. Prog. 83(2}, 53--62.
10. Zabetakis, M. G. (1967). Safety with Cryogenic Fluids, Plenum Press, New York.
11. Witcofski, R. D., and Chirivella, J. E. (1984). Experimental and analytical analysis of the
mechanisms governing the dispersion of flammable clouds formed by liquid hydrogen spills, in
Proceedings ofthe World Hydrogen Energy Conference IV (T. N. Veziroglu, W. D. Van Vorst, and
J. H. Kelley, eds.), Pergamon Press, Elmsford, New York.
12. Stewart, W. F., Dewart, J. M., and Edeskuty, F. J. (1990). Safe venting of hydrogen, in Hydrogen
Energy Progress VIII (T. N. Veziroglu, ed.), Pergamon Press, New York.
13. Custer, R. L. P., and Bright, R. G. (1974). Fire Detection: State-Of-The-Art, NASA Lewis Research
Center Report NASA CR-134642, Cleveland, Ohio.
14. Bowen, T. L. (1975). Investigation of Hazards Associated with Using Hydrogen as a Military Fuel,
Naval Ship Research and Development Center Report 4541, Bethesda, Maryland.
15. Ordin, P. M. (1974). Review of hydrogen accidents and incidents in NASA operations, in
Proceedings ofthe Ninth Intersociety Energy Conversion Engineering Conference, pp. 442--453,
American Society of Mechanical Engineers, San Francisco, California.
16. Hardee, H. C., and Lee, D. O. (1977178). A simple conduction model for skin burns resulting from
chemical fireballs, Fire Res. 1, 199.
17. Weintraub, A. A. (1965). Control of Liquid Hydrogen Hazards at Experimental Facilities, Health
and Safety Laboratory Report HASL-160, U.S. Atomic Energy Commission, New York.
18. Reider, R., Otway, H., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249-261.
19. Brewer, G. D. (1991). Hydrogen Aircraft Technology, CRC Press, Boca Raton, Florida.
20. National Fire Protection Association (1994). Liquefied Hydrogen Systems at Consumer Sites,
National Fire Protection Association Report NFPA 50B, Quincy, Massachusetts.
21. Edeskuty, F. J., Reider, R., and Williamson, K. D., Jr. (1971). Safety, in Cryogenic Fundamentals,
(G. G. Haselden, ed.), Chap. 11, Academic Press, London.
Chapter 8
Combustion Properties
Under the right circumstances, almost any property of a substance can relate to its
safety. However, there are a number of properties that directly relate to the
possibility of a fire or explosion hazard when dealing with combustible cryogens.
In this chapter we will discuss these properties as they pertain to hydrogen and
methane [including liquefied natural gas (LNG)].
Table 8.1 lists some properties of interest in the discussion of safety for
hydrogen and methane and compares them with those of gasoline. 1,2
8.1. DEFLAGRATION
With hydrogen or methane, as with many other flammable gases, with the
proper conditions, combustion can occur in either of two different ways, deflagra-
tion or detonation. A simple combustion, or deflagration, occurs when a portion of
a gas mixture, within a combustible composition range, is heated to its ignition
temperature. At this point combustion commences, and the heat released is suffi-
cient to raise the temperature of the adjacent gas mixture to its ignition temperature.
The reaction can thus propagate through the mixture in the form of a flame front
that can travel throughout the extent of the combustible mixture. The rate of this
reaction is controlled by heat transfer, and deflagration flame velocities are of the
order of a meter per second.
The limits of flammability in air define the range of gaseous fuel concentra-
tions in air at which the homogeneous mixture will be capable of being ignited and
will propagate a deflagration flame. These limits are usually determined experi-
mentally by observing the upward propagation of a flame in a vertical tube. 1 In a
gravitational field, buoyancy exerts an influence, with the result that flame propa-
gation in a downward direction is more difficult than upward propagation. Conse-
quently, near the fuel concentration limits for combustion as described above, the
combustion usually will not be complete throughout the combustible mixture. For
a more narrow concentration range, combustion can proceed in any direction, and
101
102 ChapterS
a Refs. I and 2.
b In mixtures with air at conditions of 10 1.325 MkPa (l atm) and 294 K (70 OF).
C For low-energy initiation; see Section 8.3.
d A range is necessary for this value because the autoignition temperature depends upon the ignition method. The values
for hydrogen and methane are taken from Ref. 2.
The diffusion velocity of a gas in air depends upon the temperature, T, and
varies as T 312. For this reason, the cold gases originating from spills of cryogenic
fuels will diffuse more slowly than these same gases at ambient temperature. From
Table 8.1 it can be seen that, at ambient temperature, hydrogen will diffuse about
4 times faster than methane and about 12 times faster than gasoline.
The buoyant velocities of the gaseous fuels represented in Table 8.1 vary with
bubble size and are also strongly dependent upon the temperature of the fuel gas.
However, in this case the velocity estimates were made for ambient-temperature
gas and for buoyant masses of a specific size. Hence the buoyant velocities listed
in Table 8.1 are useful mainly for demonstrating their relative values. Hydrogen's
higher diffusion velocity and buoyancy make it easier for hydrogen to reach greater
distances more quickly but also contribute to its ability to dissipate to below
combustible limits more quickly. When all of the properties in Table 8.1 are
compared, it becomes evident that it is not possible to rank these fuels according
to safety, because various possible accident scenarios can illustrate situations in
which anyone of these fuels will be the safest or the most hazardous.
The autoignition temperature in air is shown in Table 8.1 as a range. The reason
for this is that this temperature depends upon the method of ignition. Hansel et al. 2
give this temperature for hydrogen and methane for three different types of ignition:
Q)
:0
<U c:
E 0
E .0>
~~
c:
o
Z
Fig. 8.1. Effects of temperature and pressure on flammability limits. 4 LFL, Lower flammability limit;
UFL, upper flammability limit.
104 ChapterS
mixture heated in a glass vessel, mixture contacting a heated Nichrome wire, and
mixture heated by a laminar-flow air jet. Heating in a glass vessel gives the lowest
ignition temperature, and the heated Nichrome wire gives the highest ignition
temperature. For the ignition of a drifting combustible cloud, the Nichrome wire
value would seem the most appropriate.
In general, the properties shown in Table 8.1 are dependent upon the local
conditions. Figure 8.1 shows that the flammability limits of a combustible gas vary
with temperature and pressure. As either pressure or temperature is decreased, the
flammability range is narrowed. In the case of pressure decrease, at a sufficiently
low pressure, the upper and lower limits coalesce, with the result that below this
pressure no mixture of fuel and air is combustible (see Fig. 8.1).
The behavior of the combustibility range is shown in a different way in Fig.
8.2, where it can be seen that as the total system pressure is lowered, the minimum
10,------r-----,------r-----~----~----~----~
~>-
~
G)
c
W
c
.Q
:1::
C
!1'
E
::J
E
'2
~ 0.1
101 kPa
0.01 +--...--+-~-+_---.-_I_-...--_+-~-+____.-_+-....._____l
o 10 20 30 40 50 60 70
Hydrogen Concentration (vol%)
Fig. 8.2. Effects of pressure and composition on the minimum ignition energy for hydrogen in air.4 The
conditions represented by the areas under the curves do not result in ignition, but in the area above the
curves, ignition can occur.
Combustion Properties 105
ignition energy (MIE) for hydrogen-air mixtures increases. 4 From Fig. 8.2 it also
can be seen that the minimum ignition energy is a strong function of the actual
composition of the mixture, reaching its minimum value near the composition of a
stoichiometric mixture. The stoichiometric mixture is that mixture for which the
quantity of fuel and oxidizer are in the correct proportion so that after the combus-
tion is complete, none of the fuel or the oxidizer remains (for an Hrair mixture,
this is 29% H2), both being completely consumed and replaced by their combustion
products.
For a mixture of methane and air, Fig. 8.3 shows the large increase in
combustibility range caused by increasing the oxygen content of the air in the
mixture. 4 For hydrogen-air mixtures, Fig. 8.4 shows the effect of replacing the
nitrogen in the air with other inert gases. As seen in Fig. 8.4, the substitution ofthe
nitrogen by argon results in easier ignition, indicated by a lower ignition energy,
whereas the substitution of nitrogen by either carbon dioxide or helium raises the
minimum ignition energy requirement. 4
For combustion proceeding through a tube, the flammable limits for hydro-
gen-air mixtures are also affected by the total system pressure as well as by the
tube diameter. Figure 8.5 shows that as pressure is lowered, the combustion range
is narrowed and that as tube diameter is decreased, the minimum pressure for
combustion to occur is raised. Figure 8.6 shows the widening of the combustible
range for methane in air as the temperature increases. Compilations of combustion
properties of hydrogen and other combustible gases are given in Refs. 4--6.
100
50
10
~ 5
>-
e'
Q)
c 1
w
c 0.5
.2
.~
c
!l' 0.1
E
~ 0.05
E
c
~ 0.01
0.005
0.001
0 10 20 30 40 50 60
Methane Concentration (vol%)
Fig. 8.3. Effect of mixture composition on the minimum ignition energy ofmethane-oxygelHlitrogen
mixtures. 4 The conditions represented by the areas under the curves do not result in ignition, but in the
area above the curves, ignition can occur.
106 ChapterS
1.0 ....-----r-----,---.-----,-----.------.,...------,
0.5
~
>-
e>
CD
c:
W
c:
....
.Q
c:
0.1
SP
E
::l
E
c 0.05
~
0.01 -t----.--t--.....---+-...,..--f-........-+----.--+--.---+--.-----4
o 10 20 30 50 60 70
Hydrogen Concentration (vol%)
Fig. 8.4. Minimum ignition energy for hydrogen in 21 % oxygen with various di1uents. 4 The conditions
represented by the areas under the curves do not result in ignition, but in the area above the curves,
ignition can occur.
1,OOO~-----....,.....------.--------r-------.
500
100
50
as
a..
C
! 10
~ 5
!
a..
1.0
0.5
0.1-+----....,....----l---....,.....---4----.----+---..,.--~
o 20 40 60 80
Hydrogen Concentration (vol%)
Fig. 8.5. Effects of pressure and tube diameter on the flanunability limits ofhydrogen in air.4 Flammable
mixtures are represented by the areas above the curves, and nonflanunable mixtures by the areas below
the curves.
100
80
/n3K
/
/"
l,..--523K
/ l,..--293K
60
'iii
Q.
C
!!?
:::l Rammable
gj
!!? Region
I
I))
Q.
40
20 ~\
~"
\ ~/'
/
o
o 4 8 12 16
Methane Concentration (vol%)
Fig. 8.6. Effect of temperature on the flammability limits for methane in air.4 Flammable mixtures are
represented by the areas above the curves, and nonflammable mixtures by the areas below the curves.
For this theoretical case, the combustion is complete, and the entire energy release
from the combustion is consumed in heating the reaction products and residual
gases. Because the reaction is completely confined, the increase in temperature is
accompanied by a pressure increase.
Actually, the Alec curve is never quite reached. Amore typical result is shown
in Fig. 8.8 by the dotted curve, which lies below the Alec curve for several reasons.
First, below 4% and above 75% hydrogen, the mixture is not within the combustible
range, so there is no combustion and, consequently, no pressure rise. Second, from
about 4% up to about 8% hydrogen, combustion takes place only in the upward
direction, and combustion is incomplete in this concentration range. Above 8%
hydrogen, the combustion can proceed in any direction, and the actual reaction
Combustion Properties 109
Fig. 8.7. Shed damage caused by hydrogen-air deflagration. (Photograph courtesy of the Los Alamos
National Laboratory.)
curve starts to rise to approach the AICC curve. Third, during the finite time of the
combustion, there is time for some heat transfer from the combustion products to
the containment walls and solid objects within the enclosure. This process removes
some of the combustion energy and decreases the pressure that is attained.
The heat capacity of the containment, and the solid objects within it, is usually
much greater than that of the combustion products, with the result that during a
confined hydrogen-air deflagration the pressure can be expected to rise rapidly over
a short interval of time (on the order of a fraction of a second to a few seconds,
depending upon the size of the containment vessel) and then decrease as heat
transfer continues, until the pressure decreases to become close to the original
pressure (over a period of tens of seconds to minutes, again depending upon vessel
size). This behavior has been confirmed by confined-combustion tests in a closed,
vertical cylindrical vessel with a diameter of 2.13 m and a height of 5.18 m. 10 Tests
performed in a larger vessel (l7-m sphere) have also verified this behaviorY
Pressure relief panels are effective in minimizing pressure increases in experimental
rooms where deflagrations are possible. The initially confined hydrogen combus-
tion in the light shed shown in Fig. 8.7 illustrates the efficacy of pressure relief for
hydrogen-air deflagrations. Investigations of the pressure rise during deflagrations
in vented enclosures and within nonuniform mixtures (gas pockets) have been
carried out and are discussed in Refs. 12 and 13.
110 ChapterS
V
8
~
0:
6 / ~
~
~
!
J
]i 4
.1::
c::
~
~
III
!
0-
iii
c::
iI:
2
~- - -
I
I
I
I
0
0 20 40 60 80
Hydrogen Concentration (vol%)
Fig. 8.8. Theoretical maximum pressure multiplication resulting from the confined combustion of
hydrogen--air mixtures. 9 The solid line shows the theoretical maximum pressure ratio (final pressure/in-
itial pressure) resulting from the adiabatic, isochoric (constant volume), complete combustion (AICC)
of hydrogen-air mixtures. Initial conditions are 101.325 kPa (l atm) and 293 K. The dotted line is
illustrative of a possible approach to an AICC. The degree of approach will depend upon the specific
reaction conditions. However, the pressure ratio given by the AICC curve will never be fully attained
because some energy will be lost from the combustion products to the walls of the containing vessel
and other solid objects that are present.
8.2. DETONATION
a Ratio of final pressure to initial pressure for a confined, stoichiometric hydrogen-air mixture, initially
at 1 atm and ambient temperature.
b For a hydrogen-air detonation starting at 1 atm and ambient temperature, a pressure multiplication by
a factor of at least 15 can be expected. However, detonation can result from a transit from deflagration
to detonation, with the possibility that the initial pressure is already increased by the previous
deflagration. In addition, reflection of shock waves can increase instantaneous local pressures, with the
result that pressure multiplication factors as high as 120 have been given in the literature (Ref. 1).
C In a detonation, pressure can rise too quickly to allow a pressure relief system to function effectively.
100,--r------r--------.--------.---------r--------,
E
.
.<
~
1i
E
III
i5 10
~c:
0
iic:
~
0
14-----~--_r----~---+----~---+----~--~----~--~
10 20 30 40 50 60
Hydrogen Concentration (vol%)
Fig. 8.9. Detonation cell diameter for a hydrogen-air mixture initially at room temperature and
atmospheric pressure. 16
circular cross section with a 43-cm diameter. 15 These studies showed that the
detonation occurs along a series of detonation cells. The smaller the dimension of
the cell, the more likely it is that detonation will occur. Detonation cell sizes were
measured by the traces left on a sooted foil, lining the floor of the test chamber. The
cell size varied with hydrogen concentration, with a minimum cell size occurring
near the stoichiometric mixture. Figure 8.9 shows a plot of the cell size versus the
hydrogen concentration. 16 For these experiments, high explosives were used to
initiate the detonations. Figure 8.10 shows the amount of explosive needed to
initiate the detonation as a function of hydrogen concentration. 16
Although this type of initiation strength will not be available in most cases, it
is of interest to note that with the use of such high-energy initiators, the range of
the detonability of hydrogen-air mixtures at 20C has been extended down to
Combustion Properties 113
\
50,000
\
10,000
\ /
~ 1,000
.9
CD
~
8
.~
V
1\1 100
~ \
!
1\ /
\ /
10
1.0 /
0.5
10 20 30 40 50 60
Hydrogen Concentration (vol%)
Fig. 8.10. Critical mass of explosive (grams of Tetryl) to initiate detonation in hydrogen-air mixtures
initially at room temperature and atmospheric pressure. 16
11.6% and up to 74.9% hydrogen by volume. 15 These studies have also determined
some useful parameters that determine whether a detonation can persist in various
geometric configurations. Some of these relationships are presented in Fig. 8.11,
which shows that for a detonation to persist in a tube with a circular cross section,
the inside diameter must be at least one-third of the cell dimension. In the case of
two wide parallel plates, the distance between the plates must be at least equal to
the cell dimension. In each case in Fig. 8.11, the geometric parameter must be at
least as large as the function of the cell size shown in the figureY
Because of the higher pressure multiplication and the rapidity of the pressure
increase, detonations are much more destructive than deflagrations. This was
illustrated by experiments involving confined hydrogen combustions in a 6.4 m by
4 m by 4.1 m (21 ft by 13.1 ft by 13.5 ft) enclosure constructed of massive concrete
114 ChapterS
(","rT)=====~FF~==========:n-'omin=
T
Aft,
Propagation Down a Cylinder
Wmin =A
oT ~
Dmin=13A Round
Tube
.L
D Dmin = 11 A Square
Tube
TL
I Wmin =11 A
T
......W-id-e-Ch-a-n-ne-I....
Fig. 8.11. The effect of geometry on propagation of detonation waves. is For each of the configurations
depicted, the minimum size for detonation to persist is given as a function of the detonation cell
dimension, which is a function of the mixture composition (see Fig. 8.9).
blocks on three sides and the top and closed on one side by a plywood panel. During
deflagrations in which less than 30 L of liquid hydrogen was spilled from a
cylindrical Dewar and ignited, the plywood panel was shattered and blown out, but
the concrete blocks were not disturbed. During a test in which 40 L was spilled and
ignited, a detonation occurred that pushed the blocks aside and the plywood was
not only blown out but was also shattered into much smaller pieces. In addition,
Combustion Properties 115
the higher pressure, caused by the detonation in the test cell, collapsed the liquid-
hydrogen Dewar. 17 Motion pictures taken of these experiments show the greater
destructive power of the detonation. However, these pictures also demonstrate that
confined deflagration can also be destructive.
REFERENCES
I. Hord, J. (1976). Is Hydrogen Safe?, Cryogenics Division, Institute for Basic Standards, National
Bureau of Standards, Boulder, Colorado.
2. Hansel, J. G., Mattern, G. w., and Miller, R. N. (1993). Safety considerations in the design of
hydrogen-powered vehicles, Int. J. Hydrogen Energy 18(9), 783.
3. Cheiton, D. B. (1964). Safety in the use of liquid hydrogen, in Technology and Uses of Liquid
Hydrogen (R. B. Scott, W. H. Denton, and C. M. Nicholls, eds.), Chap. 10, Pergamon Press,
Oxford.
4. Benz, F. J., Bishop, C. v., and Pedley, M. D. (1988). Ignition and Thermal Hazards of Selected
Aerospace Fluids, NASA Lyndon B. Johnson Space Center, White Sands Test Facility Report No.
RD-WSTF-OOOI, Las Cruces, New Mexico.
5. Coward, H. F., and Jones, G. W. (1952). Limits of Flammability of Gases and Vapors, U.S. Bureau
of Mines Bulletin 503, U.S. Government Printing Office, Washington, D.C.
6. Zabetakis, M. G. (1965). Flammable Characteristics of Combustible Gases and Vapors, U.S.
Bureau of Mines Bulletin 627, U.S. Government Printing Office, Washington, D.C.
7. Reider, R., Otway, H., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249.
8. Bowen, T. L. (1975). Investigation of Hazards Associated with Using Hydrogen as a Military Fuel,
Naval Ship Research and Development Center Report 4541, Bethesda, Maryland.
9. Sherman, M. P., Baer, M. R., and Griffiths, S. K. (1981). Deliberate ignition and water fogs as H2
control measures for Sequoyah, Proceedings of the Workshop on the Impact of Hydrogen on Water
Reactor Safety, Albuquerque, New Mexico, January 26-28, 1981, Vol. IV, pp. 85-124, Sandia
National Laboratory Report NUREG/CR-20 17, SANDSI-066IAN.
10. Torok, R., Siefert, K., and Wachtler, W. (1983). Hydrogen Combustion and Control Studies in
Intermediate Scale, Electric Power Research Institute Report EPR! NP-2953, Palo Alto, Califor-
nia.
II. Edeskuty, F. J., Haugh, J. J., and Thompson, R. T. (1986). Safety aspects oflarge-scale combustion
of hydrogen, in Hydrogen Energy Progress VI (T. N. Veziroglu, N. Getoff, and P. Weinzierl, eds.),
pp. 147-158, Pergamon Press, New York.
12. Cubbage, P. A., and Marshall, M. R. (1972). Pressures generated in combustion chambers by the
ignition of air-gas mixtures, in Chemical Engineering Symposium Series, No. 33, pp. 24-31,
Institute of Chemical Engineers, London.
13. Sibulkin, M. (1982). Pressure rise generated by combustion of a gas pocket, Combustion Flame
38,329.
14. Sherman, M. P., Tieszen, S. R., and Benedick, W. B. (1989). The Effect ofObstac1es and Transverse
Venting on Flame Accelerations and Transition to Detonation for Hydrogen-Air Mixtures at Large
Scale, Report NUREG/CR-5275, SAND85-1264, Sandia National Laboratories, Albuquerque,
New Mexico.
15. Stamps, D. w., Benedick, W. B., and Tieszen, S. R. (1991). Hydrogen-Air-Diluent Detonation
Study for Nuclear Reactor Safety Analysis, Report NUREG/CR-5525, SAND89-2398, Sandia
National Laboratories, Albuquerque, New Mexico.
116 ChapterS
16. Lee, J. H., Knystautas, R., Guirao, C. M., Benedick, W. B., and Shepherd, J. E. (1982).
Hydrogen-Air Detonations, Proceedings of the Second International Conference on the Impact
of Hydrogen on Water Reactor Safety, pp. 961-1005, Sandia National Laboratories Report
NUREG/CP-0038, EPR! RP 1032-35, SAND 82-2456, Albuquerque, New Mexico; see also
Guirao, C. M., Knystautas, R., and Lee, J. H. (1989). A Summary of Hydrogen-Air Detonation
Experiments, Sandia National Laboratories Report NUREG/CR-4961, SAND87 -7128.
17. Zabetakis, M. G., Furno, A. L., and Perlee, H. E. (1963). Hazards in Using Liquid Hydrogen in
Bubble Chambers, U.S. Bureau of Mines Report oflnvestigations 6309, U.S. Department of the
Interior, Bureau of Mines, Washington, D.C.
Chapter 9
Oxygen Hazards
Under the proper conditions of pressure, oxygen can be a liquid over a very
wide range of temperature. The triple-point temperature and pressure are 54.35 K
117
118 Chapter 9
and 0.15 kPa (1.14 Torr), respectively. The critical-point temperature and pressure
are 154.58 Kand 5.04 MPa [731 psi (absolute)], respectively? The density of LOX
at standard atmospheric pressure is 1140 kg/m3 (71.1 Ib/ft 3 ) (see Table 1.1), and
this density limits the quantity that can be transported over the highways because
of weight restrictions. The high density is also a cause for concern in that during
flow of liquid oxygen at a high rate, a rapid closure of a valve could rupture or
damage a pipeline by the resulting "water hammer" effect.
With respect to safety, the greatest concern in the handling of oxygen is its
capability to enhance the speed and vigor of combustion. Although oxygen can be
mixed with combustible substances without reacting, the resulting mixture is easily
ignited and may react explosively in many cases. Another concern is the ability of
oxygen to permeate porous materials, especially clothing, enabling them to bum
much more rapidly when ignited. The presence of substances containing hydrocar-
bons, such as some lubricants and solvents, in either gaseous or liquid oxygen
presents an obvious hazard.
Contaminants in LOX may be in solution, if present in amounts less than that
allowed by the solubility limit. When present to an extent exceeding that limit, the
contaminants will usually precipitate as a solid. The presence of a combustible solid
presents a greater hazard of fire or explosion. Solid hydrocarbons in LOX can react
explosively when subjected to friction, shock, or impact. 3 Most solid hydrocarbon
a Ref. 3.
Oxygen Hazards 119
impurities are less dense than LOX and will tend to float on the liquid surface. They
may give evidence of their presence by forming a ring of solid material around the
interior of the container wall near the liquid surface.
Methane is highly soluble in LOX, and the higher aliphatic hydrocarbons are
less so, with their solubility decreasing as the number of carbon atoms in the
hydrocarbon molecule increases. The solubilities of several hydrocarbons in LOX,
as well as their lower flammability limits, are given in Table 9.1. 3 Most solvents
are solids at the NBP temperature of oxygen.
In addition to the hazard of unwanted combustion, contamination of oxygen
can also make it hazardous or useless in its subsequent application. Fuel cells and
breathing apparatus also have stringent limitations on impurities, and oxygen purity
requirements 3 for these applications are given in Table 9.2.
Contaminants can be introduced in the production of LOX or in its storage,
handling, or use. Exposure to the atmosphere can introduce contamination. Al-
though the major constituents of air might not present any additional hazard, air
frequently contains traces of other substances such as hydrocarbons. Even if present
only in the low parts per million concentration range, such contaminants can
accumulate until they can present a major hazard.
As shown in Table 9.1, acetylene is only slightly soluble in LOX. Acetylene
is a very reactive compound (having a triple carbon--<:arbon bond). For this reason,
its presence in oxygen is generally limited to 0.05 ppm (mole basis) or less. 3
Requirement
a Ref. 3.
b For Grade A oxygen, all other impurities, including inert gases and nitrogen, not to exceed 30 ppm.
120 Chapter 9
o 2 4 6 8 10
Impact Energy (kgm)
Fig. 9.1. Effect ofliquid-nitrogen dilution on impact sensitivity ofHT-424 adhesive in liquid oxygen
(LOX).6
on the same material, along with the energy input for those ignitions, allows the
material to be ranked according to its sensitivity to oxygen. Samples should be
configured according to ASTM D2512.4 for testing in LOX and according to
ASTM G86 for tests in gas.
Results from the drop test can show the increase in sensitivity that occurs with
increasing oxygen concentration from that in normal liquid air to that in pure
oxygen. This is illustrated in Fig. 9.1, which shows the behavior of an adhesive to
be essentially insensitive to a liquid air with 20% oxygen while at higher oxygen
concentrations the dramatic increase in sensitivity becomes obvious. 6
The pneumatic impact test subjects the sample to be tested to a high-velocity
stream of oxygen, air, or an oxygen-enriched mixture of these fluids. Again, by
Oxygen Hazards 123
varying the composition and velocity of the impacting stream, ignitions can be
noted and comparisons made.
In the friction test, test specimens are fastened to the ends of two hollow
cylinders and rubbed against each other by holding one of the cylinders fixed and
rotating the other cylinder. Test variables include oxygen pressure, loading, and
rubbing velocity. The parameter for ranking the samples is the product of the total
load divided by the area of contact between the two specimens times the velocity
of rubbing.
The autoignition test measures the minimum temperature at which the speci-
men will ignite in oxygen or in an oxygen-enriched atmosphere. The temperature
in the test vessel is increased until ignition occurs.
In the particle impact test, the test specimen is subj ected to a stream of oxygen
containing entrained particles. Ignition conditions permit the ranking of the sam-
ples. 4
9.3.1. Metals
All metals except gold, platinum, and other noble metals are combustible in
oxygen under the proper conditions. Important factors to consider in the use of a
metal in oxygen service include its composition, surface conditions, thermal
characteristics, density, geometry, and physical and mechanical properties. Also of
importance are the characteristics of the metal's oxide coating, such as its compo-
sition, adherence, and density, and the metal's thermal properties, as well as system
and dynamic conditions such as oxygen pressure and temperature, flow velocity,
heat input and removal rate, quantity and intensity of ignition source, and system
cleanliness.
There are many metals that have been safely used in LOX service. The
selection of a particular metal should be made with consideration of the actual use
124 Chapter 9
Table 9.4. Combustion Rate for Metal Rods in Oxygen at 1 atm Pressurea
a Ref. 3.
b Rods 1.59 mm (1116 in.) to 4.76 mm (3116 in.) in diameter.
C These materials did not propagate combustion in 1 atm oxygen.
Oxygen Hazards 125
9.3.2. Nonmetals
Nonmetals that are often required for use in oxygen systems include such
materials as plastics, elastomers, lubricants, adhesives, and fabrics. In an oxygen
system, the use of nonmetals that are not completely oxidized is a cause for concern
because of their potential for reacting with the oxygen. Compared to metals,
nonmetals have lower ignition temperatures, thermal conductivities, and heat
capacities, and thus they are easier to ignite. The ignition temperature of nonmetals
is highly dependent upon oxygen concentration and pressure.
The low ignition temperatures of polymeric materials make them susceptible
to ignition by the adiabatic compression heating of oxygen upon pressurization. 4
Usually, the heat capacity of the solid part of the system is sufficiently great that it
could absorb the compression heating so that only a small increase in temperature
would occur. However, in the case of rapid pressurization, the heat transfer is
usually far too slow to allow the solid components to absorb the heat. Thus, unless
the compression is done very slowly, the gas being compressed into the storage
cylinder will heat significantly and could reach a sufficiently high temperature to
cause the ignition of some nonmetals. For this reason, it is important that oxygen
systems containing such materials be pressurized slowly.
All polymers will bum in oxygen. Nylon and Mylar are not normally recom-
mended for oxygen service. However, a few nonmetallic materials with higher
ignition temperatures (up to 500C) are resistant to ignition. Polymeric materials
that are most resistant to reaction with oxygen are the fluorocarbon plastics and
elastomers. Elastomers frequently used in oxygen systems are fluorinated com-
126 Chapter 9
pounds such as Viton and Fluorel. Frequently used plastics are the semicrystalline
types, such as polytetrafluoroethylene (PTFE Teflon), fluorinated ethylene propyl-
ene (FEP Teflon), and polychlorotrifluoroethylene (PCTFE, Kel-F 81), and amor-
phous polymers such as polyimides (Vespel SP21).4
Table 9.5 shows minimum ignition temperatures for selected plastics and
elastomers,3 and Table 9.6 shows similar data for lubricants, adhesives, and fabrics. 3
Table 9.7 gives combustion rates for selected nonmetals. 3
a Ref. 3.
b Not recommended for oxygen service; included for comparison only.
Oxygen Hazards 127
Minimum ignition
Material temperature (K)
Lubricants
Tetrafluoroethylene (TFE) lubricant 778
Chlorotrifluoroethylene (CTFE) grease 773
Halocarbon grease 25-10 704
Halocarbon oil 13-21 700
Oxyweld64 683
Silicone grease 643
Adhesives
Fused TFE 738
Oxyseal (2) 620--633
Epoxy (Armstrong A-6) 583
Fabrics
Nomex 763
Orion 703
Nylon 633
Dacron 583-663
a Ref. 3.
Material 21% Oz, I atm 100% 0z, 0.2 atm 100% 0z, I Atm
Cotton 6.35 2.54 18.8
Dacron 1.78 2.29 5.84
Epoxy 0.30
Neoprene 0.25 1.02
Nomex 1.32 0.79 2.44
Nylon (fabric) 0.81 1.17 2.59
Polyethylene 0.15 0.69
Polyvinyl chloride 0.76 2.54
Polyurethane 1.42 1.78
Silicone 0.51 2.79
Velcro 0.61 1.22
a Ref. 3.
128 Chapter 9
Effective cleaning will eliminate loose scale, rust, dirt, weld splatter and
welding flux, particles, films, greases, oils, and other unwanted matter. Equipment
intended for use in oxygen systems must be cleaned of all foreign substances, both
to eliminate the possibility of unwanted reaction with the oxygen and to prevent
contamination of the oxygen that could render it hazardous or useless for its later
use. Before being placed in service, any equipment that might come into contact
with gaseous or liquid oxygen must be cleaned according to established proce-
dures. 8 Such items include liquid or gas storage vessels, either stationary or for
transport, heat exchangers, piping, fittings, valves, pressure regulators, and instru-
mentation. All contaminants that could cause malfunctions, fires, or explosions
must be completely removed. Films of grease, oil, or other organic materials
(including fingerprints) must be eliminated. Particles that could cause clogging of
flow passages, such as scale, rust, dirt, weld spatter, or welding flux, must be
removed. Also, none of the cleaning agents should remain after the cleaning process
is complete, and precautions must be taken to ensure that no recontamination can
occur before the item is placed in service.
Whenever possible, all items should be disassembled for cleaning ifthere is a
possibility of either a contaminant or one of the cleaning agents remaining in the
system in dead ends or other difficult-to-reach places. The method of cleaning must
be established beforehand to assure that all piping dead ends and branches are
properly cleaned. Methods of testing for satisfactory cleanliness must be estab-
lished beforehand. No one cleaning procedure can be satisfactory for all situations.
The proper cleaning procedure will depend upon the type of contaminant, the
location and degree of contamination, the geometry of the piece to be cleaned, and
the base material of the part to be cleaned. A typical cleaning procedure might
include such steps as mechanical cleaning (brushing or gas blasting), steam clean-
ing or cleaning with hot water and detergent, alkaline (caustic) cleaning, acid
cleaning, solvent washing (including ultrasonic), vapor degreasing, rinsing, drying,
and purging. 8 In all cases, the process selected must be compatible with the material
being cleaned and the contaminant being removed.
Precleaning is intended to remove gross amounts of foreign material such as
scale, dirt, solid objects, and hydrocarbons. Removal may be accomplished by such
processes as sweeping, vacuuming, swabbing, blast cleaning, wire brushing, or
grinding.
Steam or hot-water cleaning is usually assisted by the addition of detergents
to remove dirt, oil, and loose scale. Most detergents are water-soluble and are best
removed by flushing with clean water. The system can then be dried by purging
with dry, oil-free air or nitrogen gas.
Caustic or alkaline cleaning can be performed by spraying, immersion, flush-
ing, or hand swabbing. The cleaning solution should be warm to hot [37.8-82.2 C
Oxygen Hazards 129
(100-180 OF)]. Cleaning agents should be chosen that do not react chemically with
the materials being cleaned. The effectiveness of the rinsing process can be
determined by testing the exiting rinse water to see when the pH of the effluent
equals that of the incoming water. The system can then be dried as above. 8
Acid cleaning is performed by immersing the object to be cleaned in a suitable
acid solution, usually at room temperature. Large areas can be flushed with a stream.
Phosphoric acid-based cleaning agents can be used with any metal. Hydrochloric
acid-based cleaning agents are recommended only for carbon steels and low-alloy
steels. These agents will remove rust, scale, and oxide coatings, and they will also
strip chromium, zinc, or cadmium platings. Hydrochloric acid should not be used
on stainless steel because it might cause stress corrosion. Chromic acid- and nitric
acid-based cleaning agents are recommended for aluminum, copper, and their
alloys. As before, the cleaning process must be followed by rinsing and drying. 8
Solvent washing is used to remove organic contaminants. Cleaning may be
done by recirculation of the solvent in a closed system or in an ultrasonic cleaner.
Upon completion of the cleaning process, the solvent may be removed by draining
and purging with dry, oil-free air or nitrogen. The purge gas should be recirculated
until all traces of the solvent are removed. A halogen leak detector may be used
with chlorinated solvents to detect any remaining solvent. The test method should
be agreed upon by the manufacturer of the equipment and the purchaser. 8
Vapor degreasing is the removal of soluble organic materials by the washing
action of solvent vapors condensing upon the surface of the equipment to be
cleaned. Typical solvents used in this process include methylene chloride, trichlo-
rofluoroethane, perchloroethylene, trichloroethane (methyl chloroform), and
trichloroethylene. All of these solvents require special safety precautions. The
appropriate Material Safety Data Sheet should be obtained from the solvent
manufacturer. It should be read and all precautions observed and in place before
any use of the solvent is undertaken. Concerns are with toxicity and combustibility.
Also, proper disposal procedures for spent cleaning solution must be followed.
Solvent removal is as indicated above for solvent washing. Carbon tetrachloride
must not be used in any cleaning process. 8
After cleaning, several inspection techniques can be used to detect residual
contaminants. Visual inspection can be made with either white or ultraviolet light
(which depends upon the ability of many organic substances to fluoresce). A wipe
test with clean white paper or a lint-free cloth can be used to detect contaminants
in areas that are not visually accessible. The area should not be rubbed sufficiently
hard to remove an oxide film, which could be confused with actual surface
contamination. The paper or cloth can then be examined under an ultraviolet light.
Oily residues can be detected by a "water break test," in which the surface is wetted
by clean water. Ifthe water shows droplets or beads, this indicates the presence of
organic contamination that must be cleaned. A solvent extraction method depends
upon the ability of the solvent to dissolve an organic contaminant. This test cannot
130 Chapter 9
be used in a system that contains components that could be attacked by the solvent. 8
In any cleaning process, the use of heat should be carried out with caution where
parts to be cleaned contain materials that might be damaged by excess heat. An
example would be parts that contain multilayer thermal insulation.
Although the permissible level of contamination will depend upon the actual
application, a typical acceptable level for particular contaminants in oxygen service
has been given8 as 500 mg/m2 . Once a satisfactory level of cleanliness has been
attained, the part should be packaged to prevent the subsequent introduction of
impurities. The cleaned part should also be labeled as having been cleaned for
oxygen service. Cleaning methods described above involve chemicals that may
require special handling and disposal procedures. Additional details may be found
in Refs. 3,4, 7, and 8.
sation of air. Furthermore, if the "liquid air" condensed in this fashion is allowed
to accumulate and then to evaporate, during the evaporation process further oxygen
enrichment can take place.
The condensation of air by liquid-nitrogen can also occur if a liquid-nitrogen
surface is exposed to the atmosphere. This process leads to a contamination of the
liquid nitrogen, and if the nitrogen is subjected to nuclear radiation-for example,
if the nitrogen is used to cool an experiment in a nuclear reactor--the nuclear
radiation flux can produce ozonides or nitrogen oxides within the liquid nitrogen.
These compounds are explosive upon warming to room temperature. On a number
of occasions, explosions have occurred in liquid-nitrogen Dewars that were warm-
ing up to room temperature after having been left open to the atmosphere while in
the radiation flux of a nuclear reactor. The explosive compounds have been
observed to have a greenish-yellow color and were located on the walls of the
containment vessel near the surface of the liquid nitrogen. Advisable precautions
include starting with pure liquid nitrogen (oxygen content below 10 ppm), trans-
ferring liquid nitrogen in closed systems, and keeping the cryostat closed and under
a positive pressure with respect to the external atmosphere. If liquid nitrogen
boil-off is repeatedly replenished, greater amounts of ozone or ozonides can be
accumulated, constituting a greater hazard. Such a concentration effect can be
prevented by providing a liquid drain and a continuous supply flow of the liquid
nitrogen or by allowing the cryostat to become completely empty and warmed to
ambient temperature before refilling. 9
9.7. OZONE
REFERENCES
I. Timmerhaus, K. D., and Flynn, T. M. (1978). Safety with cryogenic systems, in Advances in
Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 23, pp. 721-729, Plenum Press, New York.
2. Compressed Gas Association (1982). Accident Prevention in Oxygen-Rich and Oxygen-Deficient
Atmospheres, CGA Pamphlet CGA P-14, Arlington, Virginia.
3. Schmidt, H. w., and Forney, D. E. (1975). ASRDI Oxygen Technology Survey, Vol. IX: Oxygen
Systems Engineering Review, NASA Report SP-3090, National Technical Information Service,
Springfield, Virginia.
132 Chapter 9
4. National Aeronautics and Space Administration (1995). Safety Standard for Oxygen and Oxygen
Systems, Guideline for Oxygen System Design, Material Selection, Operation, Storage, and
Transportation, NASA Report NSS-1740.15, Office of Safety and Mission Assurance, Washing-
ton, DC.
5. Lucas, W. R., and Riehl, W. A. (1960). An Instrument for the Determination ofImpact Sensitivity
of Materials in Contact with Liquid Oxygen, ASTM Bulletin No. 244, American Society for
Testing and Materials, Philadelphia, Pennsylvania, pp. 29-34.
6. Key, C. F. (1972). Compatibility of Materials with Liquid Oxygen-Vol. I, National Aeronautics
and Space Administration Technical Memorandum NASA TM X-64711, George C. Marshall
Space Flight Center, Alabama.
7. Hord, J. (1971). Safety with cryogenic oxygen and nitrogen systems, in Technical Manual of
Oxygen/Nitrogen Cryogenic Systems (A. F. Schmidt, ed.), Chap. 4, U.S. Air Force Report NAVAIR
06-30-501, U.S. Air Force.
8. Compressed Gas Association (I985). Cleaning Equipment for Oxygen Service, CGA Pamphlet
G-4.1, Arlington, Virginia.
9. Gault, J. D., Logan, K. w., and Danner, H. R. (1973). Ozone formation by the radiolysis ofliquid
nitrogen: Calculation and measurement, Nucl. Safety 14 (September-October), 446.
10. Sax, N. Irving (I 984). Dangerous Properties ofIndustrial Materials, Van Nostrand Reinhold, New
York.
II. Kaye, S. M. (1978). Encyclopedia ofExplosives and Related Items, Vol. 8, U.S. Army Armament
Research and Development Command, Dover, New Jersey.
Chapter 10
Slush Hydrogen
Although slush hydrogen has been studied for about three decades, its use on a
larger scale has become of greater interest because of its importance to aerospace
applications such as the National Aero-Space Plane (NASP). This chapter discusses
briefly the properties and characteristics of slush hydrogen that can influence the
safety of its handling, the nature of potential safety hazards arising from these
properties, and the design and operational considerations needed to make safe the
operation of slush-hydrogen systems. 1 In some cases, the safe handling of slush
hydrogen will require the further elucidation of some safety problems. A discussion
of safety problems that need further research, either analytic or experimental, or
both, is given in Chapter 12.
For the use of hydrogen as a fuel, slush hydrogen offers two advantages over
liquid hydrogen. First, slush hydrogen has a greater density than liquid hydrogen,
the low density of which is a disadvantage when large quantities of hydrogen are
to be transported, especially in aerospace applications. The density of slush hydro-
gen that is 50% solid by mass is 15% greater than that ofliquid hydrogen at its NBP
(see Table 10.1). Second, if the refrigeration available in the cold hydrogen is to be
used for a cooling function, slush hydrogen (50% solid by mass) affords an
additional 18% refrigeration capacity compared to that available from the evapo-
ration of liquid hydrogen at its normal boiling point.
Both of these advantages are of great importance in aerospace applications.
The increased density of slush hydrogen affords the possibility of decreasing the
tankage-to-fuel mass ratio, thus enhancing the payload capacity. The increased
cooling capacity of slush hydrogen becomes more important as the velocity of the
vehicle within the atmosphere is increased.
133
134 Chapter 10
a Ref. I.
b Abbreviations: NBP, normal boiling point; TP, triple point.
C Relative to liquid hydrogen at NBP.
Melting Line
SOUD UQUID
~
~
!!? Liquid Vapor
a..
Pressure CP
VAPOR
Temperature
Fig. 10.1. General phase diagram (pressure vs. temperature). 2 TP and CP represent the triple point and
the critical point, respectively.
Slush Hydrogen 135
Several of the physical properties of slush hydrogen can influence the safety
of operation of one or more of the systems necessary for its use. These systems
include those for production, transfer, transport, storage, and upgrading or replen-
ishment of the solid fraction. The properties considered in the following sections
are those that are of the greatest interest in discussing the safety implications of
handling slush hydrogen.
Solid
Solid and
Liquid
1
Solid and Vapor
Fig. 10.2. General phase diagram (temperature vs. entropy)? Point I represents 100% solid, point 2 the
triple point, and point 3 saturated vapor at the triple-point temperature.
136 Chapter 10
mixture within the container will then depend upon the relative proportions of each
of the three phases.
Two properties of slush hydrogen that obviously could contribute to the
existence of safety hazards are the lower vapor pressure (subatmospheric) at the TP
and the greater density, which monotonically increases as the temperature ofliquid
hydrogen is lowered from the NBP of equilibrium hydrogen (20.27 K) to the TP
(13.80 K) and further increases upon freezing. These density increases upon cooling
and freezing imply a correspondingly significant increase in volume that the
containment system must accommodate upon melting of the solid phase and/or
warming of the liquid phase above the slush temperature. Table 10.1 summarizes
values of these properties. Values are included for 50% solid-liquid mixtures both
by mass and by volume to illustrate the small, but finite, difference between these
two quantities.
200
N~P
V
100
/
V
/
/
V
I
10
TP
5
13 15 17 19 21
Temperature (I<)
Fig. 10.3. Vapor pressure of parahydrogen vs. temperature, from the triple point (TP) to the normal
boiling point (NBp). 3
Slush Hydrogen 137
1~'-------------r------------.-------------.-----'
1~~------------~------------~---------7L-~----~
"iii"
a. ~
C
!
~
!
a.
!
200
l00~~~-.--~~--~--~-r--+-~--~--~-+--~~
20 22 24 26 28 30 32 34
Temperature (I<)
Fig. 10.4. Vapor pressure of parahydrogen vs. temperature, from the normal boiling point (NBP) to the
critical point (CP).
138 Chapter 10
500
100 ~
v----
V
V
/
/
10
1
10 15 20 25 30 35 40 45 50
Temperature (K)
Fig. 10.5. Melting pressure for parahydrogen vs. temperature, above the triple point (TP).3
Slush Hydrogen 139
1.4
V
1.2
1.0
~0.8 /
~
~
~
~ 0.6
a.
0.4
V
L;mp"~,,
0.2
0.0
13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5
Temperature (K)
Fig. 10.6. Melting pressure for parahydrogen vs. temperature, from the triple-point pressure to the
critical-point pressure. 3
maintained in the liquid layer so that the upper surface of the liquid layer can remain
at a temperature at which its vapor pressure is higher than that of the slush-hydrogen
region.
Heat of transitionC
Phase changeb [Jig (Btullb)]
Solid-liquid (TP) 58.23 (25.03)
Solid-vapor (TP) 507.39 (218.1)
Liquid-vapor (TP) 449.16 (193.1)
Liquid-vapor (NBP) 445.59 (191.6)
Helium, liquid-gas (NBP)d 20.3 (8.7)
a Ref. 1.
b Abbreviations: TP, triple point; NBP. nonnal boiling point.
C Additional data on the thennodynamic properties ofparahydrogen
in the temperature range from I K to 22 K are given by Mullins
eta/. 4
d Included for comparison purposes.
3X10 19
/
V
E
u
2X10 19
g
f
'til
/
'i
II:
~
&i
iii
V
1X10 19
/
o
o 20 40 60 80
Voltage (V)
(-dx/dt) = kx;2
where x is the concentration of orthohydrogen and k is the rate constant,6 with k
having been determined to be equal to 0.01l4/h.7 The spontaneous conversion of
orthohydrogen to parahydrogen continues even in the solid state, where the con-
version rate may be even greater than it is in the liquid. 8
The conversion rate is sufficiently slow that if normal ambient-temperature
hydrogen is liquefied, the resulting liquid is of approximately the same composition
as the initial ambient-temperature gas (75% orthohydrogen) and will have an
increased evaporation rate because of the heat release by the slow conversion to
142 Chapter 10
100
80
c:
Q)
~
-g,
;
.t::
a. 60
'E
~Q)
a.
40
~
20
o 100 200 300
Temperature (K)
parahydrogen. (About 50% will be lost in a week.) Thus, for efficient storage,
commercial liquid hydrogen is converted to the parahydrogen form during the
liquefaction process. A parahydrogen concentration of at least 95% is usually
guaranteed by commercial liquid-hydrogen suppliers, although this value can be
higher in the delivered product. The equilibrium mixture of the two forms of
hydrogen at 20.3 K is 99.8% parahydrogen.
1.5~--------+-~+-------~--+-------~~~~~------~
0.5+---F-hH---+-----------+-------------l------------1
O~~~--~~-+~--~~~~--~~~~--~~~~--~
o 2 3 4
Percent Helium in Liquid Hydrogen (mol%)
Fig. 10.9. Liquid portion of the phase diagram of the hydrogen-helium system, showing the solubility
of helium in the hydrogen liquid phase. II
144 Chapter 10
In order to have the safest operation, it is necessary to have the safest possible
system and to operate it in the safest way. Wherever possible, it is desirable to
provide protection against safety hazards within the design of the system. This,
along with sufficient operator training and well thought-out procedures, can ensure
the safest operation.
errors. In situ analysis would be desirable, but the method of doing this will have
to be developed.
fraction can be expected to decrease at the rate of about 0.5% per day in a well-built
storage Dewar. This decrease will be caused by the heat leak into the Dewar and
the residual orthohydrogen-to-parahydrogen conversion taking place spontane-
ously in the stored fluid. To preclude this decrease in solid fraction and! or to upgrade
the solid fraction above the level at which it was transferred into the storage Dewar,
a replenishment or upgrading process is desirable.
SOPs must then be supplemented by checklists covering each phase of the opera-
tion, including contingency checklists prescribing the proper response to possible,
but unintended, situations that could occur during operation of the system. Obvi-
ously, the checklists must be written by those who not only are cognizant of good
safety practices but also have a detailed knowledge of the actual design of the
system and fully understand its operation. This means that the checklists should be
written by personnel at the operational site and will be site-specific. The input of
the operating engineers and technicians is valuable in the writing of these checklists,
both because of their intimate knowledge of the system and its responses as well
as because their participation will assist these same people in their training in the
safety of operation of the system.
In slush-hydrogen systems there is always the possibility of the existence of a
negative pressure with respect to the external atmosphere. F or this reason, a periodic
warming of the system to a temperature above 90 K is advisable. Such a procedure
will permit the detection of air intrusion by analysis of the residual gas and thus
indicate whether any additional purging is needed. Operational procedures should
always be planned to preclude air intrusion.
solid particles) of 0.45 mls (1.5 fils) to as high as 13.7 mls (45 fils). For flows with
a solid mass fraction of 0.3, the pressure drop was less than that with TP liquid
hydrogen for flow rates less than 3.66 mls (12 fils). With higher solid mass fractions,
the pressure drop was as much as 20% greater than for TP liquid hydrogen.27
Flow rates must be sufficient to maintain the integrity of the slush without
allowing any settling of the solid particles that would cause them to block either
the line itself or any side entrances such as for instrumentation ports or relief valves.
Proper system design must consider the sizes and orientations of transfer system
components and should be able to minimize any settling problems.
10.5. CONCLUSION
REFERENCES
I. Edeskuty, E J., Stewart, W. E, and Mann, D. B. (1991). Slush Hydrogen Safety, NASP Technical
Memorandum 1145, NASA Langley Research Center, Langley, Virginia.
2. Roder, H. M. (1977). The Thennodynamic Properties of Slush Hydrogen and Oxygen, NBSIR
77-859, U.S. National Bureau of Standards, Boulder, Colorado.
3. McCarty, R. D., Hord, J., and Roder, H. M. (1981). Selected Properties of Hydrogen (Engineering
Design Data), NBS Monograph 168, U.S. Department of CommercefU.S. National Bureau of
Standards, Washington, D.C.
4. Mullins, J. C., Ziegler, W. T., and Kirk, B. S. (1961). The Thennodynamic Properties of
Parahydrogen from I to 22 K, Technical Report No.1, Project No. A-593, Engineering Experiment
Station, Georgia Institute of Technology, Atlanta, Georgia.
5. Willis, W. L. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
6. Scott, R. B. (1988). Cryogenic Engineering, Met-Chern Research Inc., Boulder, Colorado.
7. Scott, R. B., Brickwedde, E G., Urey, H. C., and Wahl, M. H. (1934). J. Chern. Phys. 2, 454.
8. Farkas, A. (1935). Orthohydrogen and Heavy Hydrogen, Cambridge University Press, Cambridge,
England.
9. Greene, N. E., and Sonntag, R. E. (1968). Solid-liquid-vapor equilibrium in the system hydro-
gen-helium, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 13, pp.
357-362, Plenum Press, New York.
10. Smith, S. R. (1952). Gas-Liquid Phase Equilibrium in the He-H2 System, Ph.D. Thesis, Ohio
State University, Columbus, Ohio.
II. Street, W. B., Sonntag, R. E., and Van Wylen, G. J. (1964). Liquid-vapor equilibrium in the system
nonnal hydrogen-helium, J. Chern. Phys. 40, 1390.
12. Laquer, H. L. personal communication.
13. Edeskuty, E J., and Williamson, K. D., Jr. (1977). Liquid hydrogen storage and transmission, in
Hydrogen: Its Technology and Implications (K. E. Cox and K. D. Williamson, Jr. eds.), Vol. II,
Chap. 3, CRC Press, Boca Raton, Florida.
14. Gu, Y., and Timmerhaus, K. D. (1994). Experimental verification of stability characteristics for
thennal acoustic oscillations in a liquid helium system, in Advances in Cryogenic Engineering (p.
Kittel, ed.), Vol. 39, pp. 1733-1748, Plenum Press, New York.
Slush Hydrogen 157
15. Ludtke, P. R. (1970). Slush Hydrogen Flow Facility, U.S. National Bureau of Standards Report
9752, Boulder, Colorado.
16. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Report to the Agena and Centaur Systems Office, Marshall Space
Flight Center, National Aeronautics and Space Administration, Huntsville, Alabama.
17. Mann, D. B., Ludtke, P. R., Sindt, C. F., Chelton, D. B., Daney, D. E., and Pollack, G. L. (1965).
Characteristics of Liquid-Solid Mixtures of Hydrogen at the Triple Point, U.S. National Bureau
of Standards Report 8881, Boulder, Colorado.
18. Sindt, C. F. (1970). A summary of the characterization study of slush hydrogen, Cryogenics, 10(5),
372-380.
19. Voth, R. O. (1978). Producing liquid-solid mixtures of hydrogen using an auger, U.S. National
Bureau of Standards Report NBSIR 78-875, Boulder, Colorado.
20. Voth, R. 0., Ludtke, P. R., and Brennan, J. A. (1990). Producing slush hydrogen with a small auger,
National Aero-Space Plane Technical Memorandum 1099, National Aeronautics and Space
Administration Langley Research Center, Langley, Virginia.
21. Waynert, J. A., Barclay, J. A., Claybaker, C., Foster, R. w., Jaeger, S. R., Kral, S., and Zimm, C.
(1988). Production of slush hydrogen using magnetic refrigeration, in Proceedings of the 7th
Intersociety Cryogenics Symposium of the ASME, Houston, Texas, Jan. 22-25, 1989 (C. E
Gottzmann, L. C. Kun, K. D. Timmerhaus, and L. Wenzel, eds.), The American Society of
Mechanical Engineers, New York.
22. Military Specification, Propellant, Hydrogen, MIL-P-2720lB (1971).
23. Compressed Gas Association (1990). CGA G-5.3, Commodity Specification for Hydrogen,
Compressed Gas Association, Arlington, Virginia.
24. Scott, L. E., Robbins, R. E, Mann, D. B., and Birmingham, B. W. (1960). Temperature stratification
in a nonventing liquid helium Dewar, J. Res. 64C(I), 19.
25. Mann, D. B., Sindt, C. E, Ludtke, P. R., and Chelton, D. B. (1966). Slush Hydrogen Fluid
Characterization and Instrumentation Analysis, U.S. National Bureau of Standards Report 9265,
Boulder, Colorado.
26. Daney, D. E., Ludtke, P. R., Cheiton, D. B., and Sindt, C. E (1968). Slush Hydrogen Pumping
Characteristics, U.S. National Bureau of Standards Technical Note 364, Boulder, Colorado.
27. Sindt, C. E, Ludtke, P. R., and Daney, D. E. (1969). Slush Hydrogen Fluid Characterization and
Instrumentation, U.S. National Bureau of Standards Technical Note 377, Boulder, Colorado.
Chapter 11
Many documents, both fonnal and infonnal, exist to advise on or specify methods
for the design, construction, and operation of cryogenic systems. These documents
are variously known as rules, guidelines, standards, codes, and regulations, and any
of them can address any facet of the handling of a cryogenic fluid. A general goal
of all of these documents is to minimize risk of injury to personnel and damage to
facilities and to promote safety by infonning all interested parties of required,
accepted, and preferable methods of proceeding when working with a cryogenic
fluid.
Although there might be more than one safe way to carry out a given task, it
must be borne in mind that most systems will consist of pieces of equipment
manufactured by different sources and also will have to interact with other systems
that might have been built under different circumstances or might be operated by
personnel from different organizations or, even within the same organization, by
workers with different backgrounds. For this reason it is both desirable and safer
to standardize methods of design, construction, and operation to the maximum
extent possible.
All of the documents described in this chapter have been generated by people
with a considerable amount of experience, and usually the infonnation within the
text of these documents represents the consensus of a number of knowledgeable
individuals. Whenever the advice is applicable, it should be seriously considered and
followed unless there is a good reason for not doing so. Deviations from established
practices frequently lead to problems, and quick fixes by inexperienced personnel have
often resulted in accidents. Some examples are described in Chapter 13.
In this chapter the less precise word "rule" will not be used. Instead, we will
focus on guidelines, standards, codes, and regulations. In general, guidelines and
standards are consensus documents that can originate from anyone of a number of
different organizations and do not have the force of law in their application. All
such documents are intended to guide operation within a given sphere of work and,
by themselves, do not have the force of law, requiring mandatory compliance. A
body having the necessary authority can make compliance to a guideline or standard
159
160 Chapter 11
mandatory, and thus they become included in a regulation. The word "code" has
been applied to both nonmandatory and mandatory documents.
The most all-encompassing authority in the United States is contained in the
Code of Federal Regulations (CFR), into which any of the above-mentioned
documents can be incorporated, thereby making compliance to them mandatory. In
addition, the individual states as well as municipalities can also add regulations.
Within this framework, organizations can make more specific requirements per-
taining to their own operations. While these latter might not have the force oflaw,
one's employment is usually contingent upon obeying these requirements.
Thus, there are many layers of safety controls that impact upon the operation
of cryogenic systems. Those that are mandatory must be obeyed, and those that are
not are still of great value and should be considered. In some cases, the multiplicity
of the various regulations can become very complicated to follow.
ties, or standards-making and -testing bodies that serve industrial, commercial, and
public needs. Organizations that originate standards include the following:
American Society of Mechanical Engineers (ASME)
American National Standards Institute (ANSI)
American Society for Testing and Materials (ASTM)
Compressed Gas Association (CGA)
Factory Mutual Engineering and Research (FM)
Instrument Society of America (lSA)
National Fire Protection Association (NFPA)
Underwriters' Laboratory (UL)
They are empowered to include advisory provisions or provisions that are intended
to become mandatory if adopted by authorized regulatory agencies.
The writing of a standard is usually initiated when a need is recognized by
members of nationally recognized organizations. The efforts involve a review of
available information, from which the scope of the proposed standard is developed.
A tentative version is usually published for review and comment by interested
persons and those affected by it. The comments are evaluated, and, if needed, a new
tentative version is prepared. Finally, the authorship committee and then a govern-
ing board both must vote to accept or reject the proposed standard. l
The ANSI defines a standard as "a generally agreed upon set of criteria
specifically designed to define a safe product, practice, mechanism, arrangement,
process, or environment based on currently available scientific and experimental
knowledge concerning the subject or scope of the standard.,,3 A key word in this
definition is "currently." As technology advances in the field of safety, to remain
effective so must the codes and standards be reviewed and modified to reflect any
necessary changes.
The ANSI is the coordinator of America's voluntary standards systems. The
ANSI also coordinates and manages representation of U.S. voluntary standards
interests in nongovernmental international standards organizations. The major ones
are the International Organization for Standardization (ISO) and the International
Electrotechnical Commission (1EC). ANSI is the official member ofboth.4
The NFPA is a nonprofit, technical and educational organization that promotes
improvements in fire protection and prevention. One of the activities of the NFPA
is the development of codes and standards to enhance fire safety. There are over
275 such standards. These standards are consensus documents that are generated
by technical committees composed of a broad range of interested groups such as
the following:
Manufacturers
Users
Consumers
162 Chapter 11
Research/testing
Special experts
Enforcers
Installers/maintainers
Labor
Insurance
The NFPA standards are reviewed and revised on a scheduled basis. Individuals
and organizations have the opportunity to present proposals for the standards
through a public adoption process. 5
Table 11.1. Selection of ASME Codes and Standards Applicable to Cryogenic Systemsa
a Ref. 6.
Guidelines, Standards, and Regulations 163
Table 11.2. Selection of Standards from the ASME Code for Pressure Piping"
a Ref. 6.
Table 11.3. Outline ofthe ASME Boiler and Pressure Vessel Codea
Section Title
I Power Boilers
II Materials
Part A Ferrous Material Specifications
PartB Nonferrous Material Specifications
PartC Specifications for Welding Rods, Electrodes and Filler Metals
PartD Properties
III Rules for Construction of Nuclear Power Plant Components
Subsection NCA General Requirements for Division I and Division 2
Division I
Subsection NB Class I Components
Subsection NC Class 2 Components
Subsection ND Class 3 Components
Subsection NE Class MC Components
Subsection NF Component Supports
Subsection NG Core Support Structures
Appendices
Division 2 Code for Concrete Reactor Vessels and Containments
IV Heating Boilers
V Nondestructive Examination
VI Recommended Rules for the Care and Operation of Heating Boilers
VII Recommended Guidelines for the Care of Power Boilers
VIII Pressure Vessels
Division 1 Rules for Construction of Pressure Vessels
Division 2 Alternative Rules
IX Welding and Brazing Qualifications
X Fiber-Reinforced Plastic Pressure Vessels
XI Rules for Inservice Inspection of Nuclear Power Plant Components
Code Cases Boilers and Pressure Vessels
Code Cases Nuclear Components
a Ref. 6.
aRef.8.
Table 11.7. Selected Standards of the National Fire Protection Association (NFPA)
Table 11.8. A Sampling of Loss Prevention Data Sheets of Factory Mutual Engineering
and Research
Loss prevention
data sheet no. Title
"Approval Guide," Factory Mutual System
1-20 Protection against Fire Exposure
1-44 Damage-Limiting Construction
2-8N Installation of Sprinkler Systems (NFPA)
5-1 Electrical Equipment in Hazardous (Classified) Locations
5-49 Gas and Vapor Detectors and Analysis Systems
7-0 Causes and Effects of Fires and Explosions
7-7 Semiconductor Fabrication Facilitiesa
7-14 Protection for Flammable Liquid/Flammable Gas Processing Equipment
7-17 Explosion Suppression Systems
7-29 Flammable Liquids in Drums and Small Containers
7-50 Compressed Gases in Cylindersb
7-52 Oxygen
7-53 Liquefied Natural Gas (LNG)
7-55112-28 Liquefied Petroleum Gas
7-83 Drainage for Flammable Liquids
7-88 Storage Tanks for Flammable Liquids
Designation Title
Aireo Industrial Gases
AIG 1157 Safety and Carbon Dioxide in the Workplace
Air Products and Chemicals, Inc.
Safetygram-2 Gaseous Nitrogen
Safetygram-4 Gaseous Hydrogen
Safetygram-5 Gaseous Helium
Safetygram-6 Liquid Oxygen
Safetygram-7 Liquid Nitrogen
Safetygram-9 Liquid Hydrogen
Safetygram-IO Handling, Storage and Use of Compressed Gas Cylinders
Safetygram-II Emergency Action in Handling Leaking Compressed Gas Cylinders
Safetygram-12 Safe Handling and Use of Air Products Compressed Gases and Equipment
Safetygram-15 Cylinder Safety Devices
Safetygram-16 Safe Handling of Cryogenic Liquids
Safetygram-17 Dangers of Oxygen Deficient Atmospheres
Safetygram-18 Carbon Dioxide
Safetygram-19 Gaseous Carbon Monoxide
Safetygram-20 Nitrous Oxide
Linde Division, Union Carbide
EM 7212 Hydrogen Systems Electrical Safety
EN-13 Venting of Hydrogen and Other Lighter than Air Flammable Gases
F-9888-Q Liquefied Atmospheric Gases--Precautions and Safe Practices
Fll-572B Establishing Liquid Hydrogen Units at Customer Sites and Filling Stations
L-3499F Safety Precautions--Oxygen, Nitrogen, Argon, Helium, Carbon Dioxide,
Hydrogen, Fuel Gases, Ethylene Oxide, Sterilant Mixtures, Specialty
Gases
SA-5 Plant Design Safety
SA-35 Plant Fire Water Protection System
a Ref. 9.
Together, ISO and lEe form the specialized system for worldwide stand-
ardization--the world's largest nongovernmental system for voluntary industrial
and technical collaboration at the international level. The results of ISO technical
work are published in the form oflnternational Standards. There are, for example,
ISO standards for the quality grading of steel; for testing of the strength of
woven textiles; for storage of citrus fruits; for magnetic codes on credit cards;
for automobile safety belts; and for ensuring the quality and performance of
such diverse products as surgical implants, ski bindings, wire ropes, and
photographic lenses-to mention only a very few. A sampling of some ISO
standards is given in Table 11.11.9
Guidelines, Standards, and Regulations 175
States can also exercise a similar type of control, although such action is not
common. Many municipalities, however, control combustible cryogens by means
of fire ordinances.
"Adoption by Reference" or "Adoption by Transcription" are two common
methods by which a standard becomes part of a regulation. "Adoption by Refer-
ence" refers to the citing of the title of the standard and publishing information only.
"Adoption by Transcription" refers to the incorporation of the standard, in whole
orin part, into the text of the regulation.
Some elements of the U.S. Code of Federal Regulations are given in Table
11.12. Listings of some of the regulations in the CFR are presented in Appendix
A in Tables A.l, A.2, and A.3, which contain pertinent items from regulations
on liquefied natural gas facilities (Table A.l)1O and cryogenic liquid tank car
tanks (Table A.2) and OSHA regulations for handling flammable and combus-
tible liquids in the work place (Table A.3). These tables are mainly useful for
showing what types of regulations exist. Because more regulations can be added
or the regulations existing at the time of this writing can be changed or modified,
the most recently published CFR should be consulted directly for the most
current information.
176 Chapter 11
Designation Title
IOCFR Energy
14CFR Aeronautics and Space
29CFR Labor
29 CFR 1910 Occupational Safety and Health
29 CFR 1910 Subpart H Hazardous Materials
29 CFR 1910.101 Compressed gases (general requirements)
29 CFR 1910.103 Hydrogen
29 CFR 1910.104 Oxygen
29 CFR 1910.106 Flammable and combustible liquids
29 CFR 1910.110 Storage and handling of liquefied petroleum gases
29 CFR 1910.1200 Hazard communication
29 CFR 1926 Safety and Health Regulations for Construction
29 CFR 1926.151 Fire prevention
29 CFR 1926.152 Flammable and combustible liquids
29 CFR 1926.153 Liquefied petroleum gas (LP-Gas)
33CFR Navigation and Navigable Waters
33 CFR 126 Handling of Class I (Explosive) Materials or Other Dangerous
Cargoes within or Contiguous to Water Front Facilities
46CFR Shipping
46CFR38 Liquefied Flammable Gases
46 CFR Subpart N Dangerous Cargoes
49CFR Transportation
49 CFR Subchapter C Hazardous Materials Regulations
49 CFR 178.57 Specification 4L; welded cylinders insulated
49 CFR 178.58 Specification 4DA; inside containers, welded steel for aircraft use
49 CFR 179 Specifications for Tank Cars
49 CFR 179 Subpart F Specification for Cryogenic Liquid Tank Car Tanks and Seamless
Steel Tanks
49 CFR 179.400 General specifications applicable to cryogenic liquid tank car
tanks
49 CFR 179.401 Individual specification requirements for cryogenic liquid tank
car tanks
49 CFR 179.500 Specification DOT-I07A; seamless steel tanks to be mounted on
or forming part of a car
49 CFR 192 Transportation of Natural and Other Gas by Pipeline
49 CFR 193 Liquefied Natural Gas Facilities: Federal Safety Standards
Guidelines, Standards, and Regulations 177
The NFPA has a standard (NFPA 52) to cover compressed natural gas (CNG)
vehicular fuel systems but does not as yet have a similar one for hydrogen-fueled
vehicles. Bulk hydrogen systems have been in common usage for several decades
and have a safe operating history. This safety record can be attributed, at least in
part, to the appreciation of the installers and operating personnel for the potential
hazards associated with hydrogen. NFPA standards 50A and 50B apply to gaseous
and liquid hydrogen, respectively. These standards cover bulk hydrogen storage
systems from the point of the local fill connection to the point where the hydrogen
enters the customer's piping system. They do not cover either the delivery vehicle
or the distribution piping. A discussion of the philosophy of these two standards is
provided by Connolly. 11
The quantity-distance separation tables are the heart of these two documents.
An important factor, which is not stated directly in these documents, is that the
catastrophic failure of the storage vessel is not considered to be a credible event.
Thus, if a storage vessel were to fail catastrophically, the separation distances might
not be sufficient to prevent serious injury or property damage. Much greater
separation distances are specified by the Department of Defense (DOD) for liquid
hydrogen used as a propellant. 12,13 Thus, we have separation distances specified for
(1) the storage of liquid hydrogen, where the main safety consideration is release
and possible burning of hydrogen in air, and (2) the use of liquid hydrogen in an
experimental or testing facility as a propellant in conjunction with an oxidizer (such
as liquid oxygen), where the primary safety consideration is pressure rupture and/or
the rapid combustion, or detonation, of a hydrogen-oxidizer mixture.
Federal regulations applying to hydrogen are embodied primarily in the
49 CFR (DOT) and 29 CFR (OSHA). The DOT portions apply to the transportation
of hydrogen, and the OSHA portion applies to its safe handling in the work place.
The Transportation Safety Act of 1974 precipitated the reorganization of the
DOT and the concomitant revision of applicable regulatory codes. Equipment
specifications and shipping and carrier regulations for gaseous and liquid hydrogen
are given in the CFR, for example, 49 CFR 179 (see Table A.2 for a partial listing).
The CFR gives the federal regulations for the transportation of gaseous and liquid
hydrogen by highway, railroad, air, and water. The DOT classifies and treats
gaseous and liquid hydrogen as a compressed, flammable gas (see 49 CFR 172.101
and 49 CFR 172-179). The proper shipping name for liquid hydrogen is "HYDROGEN,
LIQUEFIED" (49 CFR 172.10 1). Air transportation of compressed hydrogen gas is
regulated by 49 CFR 172-178. Transportation of compressed hydrogen gas by
water is regulated by 49 CFR 172-179. Liquid hydrogen currently cannot be
shipped by either air or water. However, by special permit from the U.S. Coast
Guard, NASA has shipped liquid hydrogen by barge from Louisiana to Mississippi.
The DOT no longer issues these special permits but grants "exemptions" to the
178 Chapter 11
11.4. CONCLUSION
REFERENCES
I. F. J. Edeskuty and N. N. Sheheen, eds. (1979). Critical Review and Assessment of Environmental
and Safety Problems in Hydrogen Energy Systems, Los Alamos Scientific Laboratory Report
LA-7820-PR, pp. 58-61, Los Alamos, New Mexico.
2. Siminski, V. J. (1987). Application of national consensus standards to pilot plant safety, Chern.
Eng. Prog. 83(1),60.
3. Anon. (1977). Safety standards, ProfeSSional Safety 1977 (August), Editorial.
4. American National Standards Institute (1982). 1982 Catalog of American National Standards,
American National Standards Institute, New York.
5. Bender, F. X. unpublished communication.
6. American Society of Mechanical Engineers (1995). 1995 ASME Publications Catalog, American
Society of Mechanical Engineers, Fairfield, New Jersey.
7. American Society for Testing and Materials (1992). Subject Index; Alphanumeric List, in 1992
Annual Book of ASTM Standards, Section 00, Vol. 00.01, American Society for Testing and
Materials, Philadelphia, Pennsylvania.
8. American Society for Testing Materials (1993). 1993 Annual Book of ASTM Standards, American
Society for Testing and Materials, Philadelphia, Pennsylvania.
9. International Organization for Standardization (1993). ISO Catalogue 1993, International Organi-
zation for Standardization, Geneva, Switzerland.
10. Liquefied Natural Gas Facilities: Federal Safety Standards, 49 CFR Part 193, Fed. Regist. 42(77),
Part m (April 21, 1977), pp. 20776-20800.
Guidelines, Standards, and Regulations 179
II. Connolly, W. W. (1966). A practical safety standard for commercial handling of liquefied
hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.), Vol. 12, pp. 192-197,
Plenum Press, New York.
12. U.S. Department of Defense (1964). Quantity-Distance Storage Criteria for Liquid Propellants,
Department of Defense Directive 4145.21.
13. U.S. Department of Defense (1984). Ammunition and Explosives Safety Standards, Department
of Defense Directive 6055.9.
Chapter 12
The controlled venting of cryogen vapors such as the normal boil-off from a
cryogenic storage Dewar is not usually a problem. However, the unintended, rapid
release caused by a leak from a system under pressure or the spill of a large quantity
of a cryogenic fluid can give rise to a serious hazard. While other hazards might
arise, such as from cold embrittlement of nearby equipment (see Chapter 3), the
major concerns are the creation of a local atmosphere that does not support life
181
182 Chapter 12
Large quantities of LNG and liquid hydrogen are being transported by ships
and barges. The transport of any cryogen, including liquid hydrogen and LNG, by
184 Chapter 12
hydrogen and for methane is similar; however, because hydrogen radiates outside
the visible (in the infrared) portion of the spectrum, the thermal energy hazard from
a hydrogen fire will be less than from a natural gas fire of equivalent energy release
because of the absorption of thermal radiation by water vapor in the air. The lack
of a visible fire, however, can increase the hazard.
Heat is transmitted from a hydrogen fire to neighboring objects by thermal
radiation and convection. Factors affecting the thermal radiation intensity on an
object near a fire include:
the absorption of thermal radiation in the atmosphere between the flame
and the object
the temperature throughout the flame
the amount of soot in the flame (soot will not be produced by burning
hydrogen, but by burning of nearby materials)
the gas composition (in addition to a hydrogen/air mixture, a hydrogen and
natural gas/air mixture is also of interest)
An investigation is needed of the fire hazards or damage potential from hydrogen
fires considering these factors. Thermal radiation fluxes from hydrogen fireballs
and flames should be measured. Radiation to a point from a cloud combustion
should be studied.
Evaluation of the consequences of a hydrogen fireball (as a function of its size,
duration, and radiation) should be further developed for protection of personnel,
facilities, and equipment.
The properties ofliquid and slush hydrogen, especially slush hydrogen's very
low vapor pressure (below atmospheric), introduce a number of safety problems,
the most significant of which is the possibility of air in-leakage.
Safety Problems Needing Further Investigation 187
container. The proper response may differ depending on the container's ability to
contain (confine) an energy release.
Plans for dealing with possible air contamination in liquid or slush hydrogen
will require answers to questions such as:
Will solid oxygen or air transfer with liquid or slush hydrogen?
Does solid oxygen or air accumulate in one location in a tank, transfer line,
valve, etc.?
What is the impact sensitivity of a solid-oxygen particle hitting a filter
screen, pipe wall, valve, etc.?
What is the effect of entrainment for a high vent rate (such as burst disk
rupture) for a solid/liquid cryogen mixture?
Will solid-nitrogen or solid-oxygen particles plug relief valves,filters, etc.?
Do solid oxygen particles conglomerate, leading to contamination buildup,
or will they be distributed throughout the system?
Will hydrogen and oxygen gases mix or accumulate in layers if a contami-
nated system is warmed to above the NBP for oxygen or to room tempera-
ture?
size. A standard is needed for the design, installation, and use of dikes around
liquid-hydrogen storage tanks. Such a standard should be based on an evaluation
of spill containment versus dispersion of a liquid-hydrogen spill. In some circum-
stances it may be preferable to channel a spill to a better place for disposal or to
have it burn there.
Another aspect of this standard should be consideration of the need for a water
cooling/deluge system for hydrogen storage systems, especially liquid and slush,
to keep the tank cool (not to put out afire); spraying of water on the vent system
must be prohibited (to avoid accumulating an ice blockage of the vent system).
Another consideration for inclusion in a hydrogen storage standard is the use
of hydrogen and flame detectors.
The standard should also address the need for protective clothing and safety
equipment for personnel. Conflicting guidelines exist regarding some personnel
protective clothing and equipment use. An example is whether or not ground straps
should be used on personnel working in the vicinity of hydrogen. Another is the
use of nonsparking tools in the vicinity of hydrogen, which some guidelines
recommend while others do not.
vessels. The inner container of a vacuum-insulated vessel can be coded and stamped
in accordance with the ASME Pressure Vessel Code. The ASME Pressure Vessel
Code addresses the thickness of the outer container of a vacuum-insulated vessel,
but some provisions of the code are not compatible with practices related to high
vacuum (such as double welding at penetrations because of the possibility of virtual
leaks), and others (such as pressure testing because of the need for external pressure)
can be difficult or expensive to achieve. Consequently, the outer container is usually
not code-stamped as is the inner container for a double-walled vessel. The proposed
standard should address the need for structural integrity and vacuum requirements,
inner tank loads on the outer tank, and external pressure testing. A greater pressure
loading of the outer tank could occur from a failure of the inner tank, and this might
dictate the design and testing requirement for the outer tank.
REFERENCES
1. Stewart, W. F., Dewart, J. M., and Edeskuty, F. 1. (1990). Safe venting of hydrogen, in Hydrogen
Energy Progress VIII (T. N. Veziroglu and P. K. Takahashi, eds.), Vol. 3, pp. 1209-1218, Pergamon
Press, Elmsford, New York.
2. Witcofski, R. D., and Chirivella, 1. E. (1984). Experimental and analytical analysis of the
mechanisms governing the dispersion of flammable clouds formed by liquid hydrogen spills, in
Proceedings of the World Hydrogen Energy Conference IV(T. N. Veziroglu, W. D. Van Vorst, and
1. H. Kelley, eds.), Pergamon Press, Elmsford, New York.
3. DeSteese, J. G., and Counts, C. J. (1982). Liquefied Gaseous Fuels Safety and Environmental
Control Assessment Program: Third Status Report, Battelle Pacific Northwest Laboratory, Report
PNL-4l72 UC.ll, Richland, Washington.
4. Dodge, B. F. (1944). Chemical Engineering Thermodynamics, McGraw-Hill, New York, pp.
297-298.
5. McCarty, R. D., Hord, J., and Roder, H. M. (1981). Selected Properties of Hydrogen, NBS
Monograph 168, U.S. Government Printing Office, Washington D.C.
6. Zabetakis, M. G. (\967). Safety with Cryogenic Fluids, Plenum Press, New York.
7. Stamps, D. w., Benedick, W. B., and Tieszen, S. R. (1991). Hydrogen-Air-Diluent Detonation
Study for Nuclear Reactor Safety Analyses, Sandia National Laboratories Report NUREG/CR-
5525, SAND89-2398, Albuquerque, New Mexico.
8. Sherman, M. P., Tirszen, S. R., and Benedick, W. B. (1989). Flame Facility, the Effect of Obstacles
and Transverse Venting on Flame Acceleration and Transition to Detonation for Hydrogen-Air
Mixtures at Large Scale, Sandia National Laboratories Report NUREG/CR-5275, SAND85-1264,
Albuquerque, New Mexico.
9. Parrish, W. R. (\985). Sampling and analysis, in LNG Measurement, A User's Manual for Custody
Transfer (D. B. Mann, ed.), Section 2.2, U.S. Department of Commerce, National Bureau of
Standards, NBSIR 85-3028, Boulder, Colorado.
10. Parrish, W. R., Arvidson, 1. M., and Labecque, L. R. (1978). Development and Evaluation of an
LNG Sampling Measurement System, U.S. National Bureau of Standards, NBSIR 85-3028,
Boulder, Colorado.
11. Lee, R. E. (1952). The Explosiveness of Solid Oxygen in Liquid Hydrogen, Cambridge Corp.
Technical Memorandum No. 19, Boulder, Colorado.
Safety Problems Needing Further Investigation 195
12. Cook, M. A., and Udy, 1. 1. (1962). Detonation Pressure of Liquid HydrogenlLiquid Oxygen,
Final Report for Contract No. NAS8-5058, George C. Marshall Space Flight Center, National
Aeronautics and Space Administration, Huntsville, Alabama.
13. Plaster, M., McClenagan, R., Phillips, M., Benz, F. J., and Ullian, 1. (1988). Detonation Properties
of Liquid Hydrogen and Liquid Oxygen, Proceedings of the 1988 JANAF Safety and Environ-
mental Subcommittee Meeting, Chemical Propulsion Information Agency Publication 485, Johns
Hopkins University Physics Laboratory, Laurel, Maryland.
14. Arthur D. Little, Inc. (1961). Final Report, Electrostatic Hazards Associated with the Transfer and
Storage of Liquid Hydrogen, Report to the Agena and Centaur Systems Office, Marshall Space
Flight Center, National Aeronautics and Space Administration, Huntsville, Alabama.
15. Cassutt, 1., Biron, D., and Vonnegut, B. (1962). Electrostatic hazards associated with the transfer
and storage of liquid hydrogen, in Advances in Cryogenic Engineering (K. D. Timmerhaus, ed.),
Vol. 7, pp. 327-335, Plenum Press, New York.
16. Willis, W. 1. (1966). Electrical conductivity of some cryogenic fluids, Cryogenics 6 (October),
279.
17. Mann, D. B., Ludtke, P. R., Sindt, C. F., Cheiton, D. B., Daney, D. E., and Pollack, G. 1. (1965).
Characteristics of Liquid--Solid Mixtures of Hydrogen at the Triple Point, U.S. National Bureau
of Standards Report 8881, Boulder, Colorado.
18. Daney, D. E., and Mann, D. B. (1967). Quality Determination ofLiquid--Solid Hydrogen Mixtures,
U.S. National Bureau of Standards Report 9701, Boulder, Colorado.
19. National Fire Protection Association (1993). Standard for Gaseous Hydrogen Systems at Con-
sumer Sites, NFPA 50A, National Fire Protection Association, Quincy, Massachusetts.
20. National Fire Protection Association (1993). Standard for Liquid Hydrogen Systems at Consumer
Sites, NFPA 50B, National Fire Protection Association, Quincy, Massachusetts.
Chapter 13
A safe system design requires that safety be considered from the very begin-
ning of the design process. Once the design is under way, it is time to consider safety
reviews. One such review is a failure analysis of the system components [this is
commonly referred to as a failure modes and effects analysis (FMEA)]. These
components will probably have come from several different suppliers, and the
designer expects them to operate safely in concert with each other according to his
specifications. Under some circumstances, anyone of these components might fail
in a number of different ways. In the case of a valve, failure could result from such
actions as failing to open or close, opening further or less than commanded, leaking
through the seat or through the packing, or operating erratically.
The examination of the system design can be performed by personnel experi-
enced in safety, but this review should be performed together with the designers
and, if possible, also the operators of the proposed system. A more formal review
197
198 Chapter 13
system was devised in England l and is now followed in several other countries.
This system is referred to as the hazard and operability study, or HAZOP.
After an accident or operational difficulty, there is usually some kind of
investigation intended to prevent a recurrence and to allow as much as possible to
be learned from the incident. However, learning from experience is usually more
costly than would have been the case if the problem could have been anticipated.
Thus, the object of HAZOP is to create some "synthetic experience" or "20/20
foresight. "
The safety review of a cryogenic system is performed by a committee consist-
ing of a cryogenic engineer, a safety expert, a designer, a project manager, and other
technical advisers as required. Each component of the system is considered indi-
vidually, and then the system is treated as a unit. First, the purpose, function, and
performance of the individual unit is stated, and guiding questions are asked to
determine the possibility of failure of a given component. If vulnerabilities are
detected, remedies are determined, and the design or specifications can be modified.
In this way, either safety hazards can be eliminated or the consequences of a mishap
can be diminished.
In addition to the type of safety review represented by HAZOP, it will
frequently be necessary to present a safety analysis report to various authorities to
assure them of the safety of proposed new projects. Other safety review procedures
such as fault tree analysis and risk analysis are valuable investigative methods.
which the authors have more than just a casual knowledge of the conditions or
causes.
A conclusion that can be drawn from this incident is that it is best not to join
separate components of a system to a common vent line when there is any
possibility of interaction. Also, with respect to the flaring of small flow rates of
venting hydrogen, this incident lends credence to the philosophy that says "if you
don't have a fire, why start one?"
An experiment was being performed to measure the sound level of a rapid flow
of hydrogen. 3 At the facility, the normal procedure was to flare any hydrogen release
greater than 0.45 kg/so The experiment was being performed in order to determine
the effect of the combustion on the acoustic field during the high-flow venting of
hydrogen. Therefore, one test was performed with flared hydrogen, and one with
unburned hydrogen.
The hydrogen entered the piping system connecting the hydrogen supply tanks
to the discharge nozzle at 23 MPa (3400 psi) and at ambient temperature. In the
case ofthe test with unburned hydrogen, the flow rate was ramped up to 55 kg/s in
13 s. That flow rate was maintained for lOs, and the flow was then ramped down.
After the flow had decreased to about 16 kg/s (in about 3 s), an unplanned ignition
occurred.
An attempt had been made to ensure the absence of ignition sources. The
hydrogen was obtained as liquid hydrogen and converted to high-pressure, ambient-
temperature gas in the storage bottles and was believed to be very pure. In addition,
the system had previously been blown down until there was no further evidence of
entrained solid particles in the effluent gas. However, it is very difficult to ensure
the absence of particulate matter in field-fabricated systems in a harsh climate.
Furthermore, the flow rates were higher than in the previous blow-down tests, and
it was estimated that the exit velocity of the hydrogen was in excess of 1200 mls.
It is believed that the ignition source was probably a static charge built up by
particulate matter in the exhaust stream or possibly a particle striking a solid object
near its discharge. One other possible ignition source could have been the rupture
of a metal rod that was supporting some instrumentation. The rod was found to be
broken after the explosion.
At the time of the ignition, approximately 900 kg (1980 lb) of hydrogen had
been vented, and it was estimated that about 10% of this amount participated in the
combustion. The closest observers, located in the open about 800 m (2625 ft) away,
did not detect a pressure wave. However, windows were rattled in a building about
3200 m (2 mi) away.
In the closer buildings, there was some superficial damage. In the concrete test
cell, a door latch was broken, and two plate glass windows were also broken. This
was at a distance of about 20 m (66 ft) from the exit ofthe nozzle. At a distance of
about 35m (115 ft), a laboratory mill-type building suffered a cracked window and
Accidents: Prevention and Examples 201
some slight bending of one of its structural members, but the damage was not
sufficient to warrant any repair. From the extent of the damage, it was estimated
that the buildings had experienced an overpressure of 1.2-2.4 kPa (0.17-0.34 psi).
Motion pictures of the explosion had been taken. These were color pictures
taken at 100 frames per second and infrared pictures taken at 96 frames per second.
From these pictures it was possible to observe that the flame front was traveling at
30 mls. This velocity is of interest because it is an order of magnitude higher than
what would have been expected from a deflagration, but almost two orders of
magnitude lower than that of a detonation.
From this incident it can be concluded that it is very difficult to eliminate all
ignition sources from rapidly venting hydrogen. Also, the experiment lends support
to the opinion that only a small part of the total amount of vented hydrogen actually
participates in a combustion like this (10% in this case). Another observation was
that the deflagration flame-front velocity can be significantly accelerated to reach
a velocity an order of magnitude higher than that of a simple deflagration, but more
than an order of magnitude lower than that of a detonation.
gauge on the tank was replaced with a new 200-psi gauge (one report indicated that
it had a much higher range). This gauge indicated zero tank pressure. Some
witnesses stated that the tank was venting through a blown rupture disk and that
there was a slight leak from the vaporizer inlet valve.
Conditions were stable and all personnel left at 9:00 P.M. However, several
people visited the site during the night and reported that conditions were satisfactory
and that there was a frost buildup on the outside of the vent pipe and around the
vaporizer inlet valve, both indicating continued venting of the H 2.
At 8:30 A.M. on Sunday, the insulation vacuum was 46.7 Pa (0.35 Torr). At 9:30
A.M., the N2 injection was stopped. To speed up H2 vaporization, the vacuutn valve
was opened slightly at 10:30 A.M. and fully opened at 11 :30 A.M. Some increase in
venting rate and frost buildup on the stack was noted, but still no reading showed
on the new tank-pressure gauge. Six witnesses were present; as conditions appeared
to be stable, all personnel left the immediate vicinity of the Dewar at 11 :54 A.M.
They were ready to enter their cars in the parking lot on the other side of a
2.4-m-high (8-ft-high) chain link fence about 15.2 m (50 ft) from the Dewar when
the Dewar exploded at 11 :58 A.M. The explosion was heard and the flame was seen
a mile away. The city fire department arrived at 12:05 P.M. and wet down the area,
although the fire seemed to be out 3-4 minutes after the explosion.
The only people near the explosion were the six in the parking lot. One of these
was not injured, but five had skin burns (some third degree), shrapnel wounds, and
blast effect wounds (punctured ear drums and impact with ground----one reported
being "scooted" across several feet of pavement). None of the injuries was serious.
The Dewar was extensively damaged. Both the inner and outer shells ofthe Dewar
were split into numerous pieces and scattered around the area. Some large pieces were
found several hundred feet from the Dewar site. AO.3 m x 0.3 m (1 ft x 1 ft) piece was
found at 366 m (1200 ft), and a piece of the aluminum inner shell, 1.5 m (5 ft) in
diameter and weighing about 86.4 kg (190 lb), was at 91.4 m (300 ft). At 45.7 m
(150 ft), the nearest wall of the main building was pushed in. All windows were
broken, and the interior furnishings were scattered ("as if a tornado had hit").
Another building about 305 m (1000 ft) away had minor damage.
The fuel source for the original fire on Saturday could have been a leaking
compression fitting in the control area of the Dewar or the vent stack drain line.
The cause of the explosion on Sunday was attributed to an Hr02 reaction by one
person, who mentioned some possible sources of contamination. However, the
dominant feeling was that breaking the vacuum was the cause of the explosion.
Exactly what happened is uncertain, but it was speculated that a partial blockage
in the vent line prevented adequate venting of the high boil-off rate after the
insulation vacuum was broken, and the resulting pressure buildup in the tank caused
its rupture. The blockage in the vent system was postulated to possibly be from
either (1) impurities in the tank contents, (2) water sprayed on the tank after the
fire, (3) water condensed from the atmosphere following the removal of the section
Accidents: Prevention and Examples 203
of the vent pipe, or (4) the nitrogen purge placed on the tank. The accident analysis
indicates that the partial blockage apparently in existence up until Sunday morning
was not so severe as to prevent the escape of reasonable amounts of hydrogen that
are normally vented. However, the remaining vent area was not adequate to handle
the increased boil-off resulting from breaking the vacuum in the insulation space.
It is also speculated that there was a blockage to the tank pressure gauge so that it
did not indicate the actual tank pressure.
Some conclusions from this accident include: (1) redundant instrumentation
is recommended to provide an adequate, and believable, indication of actual
operating conditions; (2) more than one vent point should be provided because the
failure of a single vent could result in damage to the equipment and injury to
personnel; (3) advance emergency planning should address appropriate actions to
be taken in the event of possible emergency conditions; and (4) no action should
be taken until the total consequences ofthat action have been thoroughly evaluated.
transfer tube and also pushed over the open end of the 50-L Dewar (with great
difficulty). A schematic of the setup is shown in Fig. 13.1a.
It was realized that with this arrangement there was no vent for the transfer
process, so a notch was cut in the end of the rubber tube where it was pushed over
the end of the metal transfer tube. It is doubtful whether this expedient could have
been very effective in that gas would have to flow in the opposite direction to the
liquid flow in a fairly small tube. However, the vent was further compromised by
pushing the metal tube so far into the rubber tube that the notch was closed off.
Transfer
Line
Rubber
Hose
l60-Liter
Dewar
50-Liter
Dewar
Dolly
The transfer was then started and had proceeded for about 15 minutes when a
loud "pop" was heard. The transfer was stopped by closing the valve on the supply
cylinder, and the two workers took cover. After about two minutes there was no
further sign of anything wrong, so one of the workers tried to remove the rubber
hose. The hose was now very stiff and could not be removed, so one of the workers
started to open the threaded connection on the supply cylinder with a wrench and
was in the process of doing so when the 50-L Dewar exploded. He was seriously
injured, and there was an undetermined amount of damage to the laboratory.
Upon further inspection, it was learned that the supply cylinder had a higher
pressure rating than had been thought. The workers thought that they were working
with a vessel at a gauge pressure of about 160 kPa [23 psi] (gauge), but the vessel
was actually operating at 1.58 MPa [230 psi] (gauge). Therefore, it was initially
believed that the higher pressure in the supply cylinder was what caused the
explosion.
However, upon further examination, this was found to be a questionable
assumption. First, three sets of calculations were made independently, two after the
accident and one made and then tested experimentally by the Dewar's manufacturer
in the 1960s.4 These calculations all indicated gauge burst pressures in the vicinity
of2.07 MPa [300 psi] (gauge), a pressure greater than any pressure available from
the supply cylinder. Second, it was estimated that during the 15-minute transfer
period about 45 L would have been transferred into the 50-L Dewar. At this point
the pressure in the supply cylinder would have decreased to about 1.24 MPa
[180 psi] (gauge), and the pressure in the 50-L Dewar would have risen to be almost
as great. When liquid is withdrawn from a cryogenic Dewar containing saturated
liquid under pressure, the remaining pressure in the Dewar can be calculated from
the first law ofthermodynamics. 5 In order to prove this point, a withdrawal test was
made using a similar Dewar, and this test verified the calculations.
An important consideration in reaching an understanding of the mechanism of
the accident is that the method of filling subjected the 50-L Dewar fill tube to a
different cooling mechanism than ordinarily would have been the case if the wand
had been used in the usual manner. When a Dewar is filled with the wand loosely
inserted in the fill tube, the cold liquid does not touch the fill tube directly. The
wand usually penetrates into the Dewar below the end ofthe fill tube, and the liquid
drops directly to the bottom of the storage sphere after it leaves the end of the wand.
Thus, the only cooling that the fill tube experiences is from the boil-off gas with
lower heat capacity and also a lower heat-transfer capability. With the fill method
used in this accident, the liquid could flow directly on the tube wall and cool it
faster. A computation of the heat transfer in this process showed that not only the
fill tube could be cooled, but also the brass spacers that fastened the outer vacuum
jacket to the top of the fill tube and, in addition, the upper cylindrical part of the
vacuum jacket around the fill tube would also be cooled. With a heat-transfer rate
of 14 W, about 10 minutes of this cooling is sufficient to cool the upper vacuum
206 Chapter 13
jacket tube to about 150 K. The outer sphere that is joined to this tube, on the other
hand, presents a much larger surface to the outside temperature, and for it to receive
the same rate of heat transfer from the external atmosphere, its temperature would
only have to drop about 4 K. Consequently, the upper tube of the vacuum jacket
can be cooled much more than the outer spherical part of the vacuumjacket. Thus,
there can exist a sharp temperature gradient across the joint between the outer
sphere and its junction with the upper tubular part of the vacuum jacket (see Fig.
13.1b). This temperature difference was shown to be adequate to break open the
nner Necktube
(Stainless Steel)
Outer Necktube
(Copper)
Joint B
Fig. 13.1b. Detail of the top ofthe 50-I Dewar shown in Fig. 13.1a.
Accidents: Prevention and Examples 207
solder joint at this junction and allow the atmosphere to enter the vacuum jacket.
Examination of the pieces of the ruptured Dewar showed a wide crack, opening
almost halfway (about 160) around this joint (joint B in Fig. 13.lb).
The normal boil-off loss of the Dewar was computed to be a little over 5.1 %
per day, equivalent to a heat input of2. 7 W. The loss was later measured on a similar
Dewar and found to be 5%. Breaking the vacuum can be calculated to increase this
loss rate by a factor of about 75, to over 200 W. If the Dewar were filled to 45 L,
this heat input can raise the Dewar pressure at the rate of 4 70 kPa ( 68 psi) per minute.
Thus, if the "pop" was indeed the cracking open of the joint in the vacuum jacket,
a period of about two minutes would be expected to be what would be needed to
raise the pressure of the 50-L Dewar to its bursting pressure. Of course, even if the
vacuum jacket had not been opened to the atmosphere, the normal heat leak would
eventually have raised the pressure to the bursting point, but that would have taken
over two hours.
If the initial "pop" had been the opening of a leak in the inner shell, the liquid
rushing into the warm vacuum jacket would be expected to raise the system to
bursting pressure much more quickly than in two minutes.
This accident is another example of the danger of quick fixes without proper
planning and without consideration of the possible consequences. Makeshift ar-
rangements should not be attempted, and training in working with cryogenic fluids
should stress the potential danger of the buildup of pressure, which, in some
circumstances, can be too rapid to permit remedial action to be taken.
destroyed, and there was some superficial damage to the laboratory. Fortunately,
there was no one in the room when the explosion occurred.
Calculations showed that the vent should have been adequate, even for the
very high venting rate that occurred. A subsequent examination of the vent pipe
showed that a foreign object had been inserted into the end of the vent pipe, probably
a screw because there was evidence of the remains ofa screw thread in the inside
of the end of the vent pipe. While no explanation was forthcoming as to the reason
for this action, it is suspected that the high rate of venting was sufficiently noisy to
disturb some other worker who thought that he/she could suppress the noise by
inserting a relatively tight-fitting screw into the end of the vent tube. However, the
guilty party could not be found.
This accident illustrates the fact that quick fixes seldom work and are fre-
quently dangerous. Also, the importance of adequate training is obvious, as such
training would have shown the first experimenter that his plan would not work, and
the second person would have realized how dangerous his or her action was.
technician installing an extra bolt that was to hold the oxygen tank's supporting
segment to the frame of the service module during initial assembly at the contrac-
tor's plant where the service module was being assembled. A second technician did
not know that an extra bolt had been installed, and when he went to remove the
segment with the oxygen tank in place, he removed the bolts that he was aware of
but left the extra bolt still attaching the segment to the frame of the service module.
The crane that was used to lift the segment was not strong enough because of the
extra load of the weight of the segment as well as the resistance of the still-attached
bolt, and the crane broke, allowing the segment to fall back a few inches onto its
mounting.
The design of the oxygen tank included a short insert piece of aluminum tubing
to connect the upper part of the fill tube to the lower, slightly offset part of the fill
tube. The short piece of aluminum tube was joined to the other parts of the tube at
both ends by Teflon bushings (sleeves). Although the vessel could be filled without
a tight connection at this point, a tight connection to the lower tube was needed to
empty the liquid during the detanking procedure that would be required later.
Unknown at that time was the fact that if all tolerances were at their limit, the
aluminum tube with its Teflon sleeves would just barely span the distance between
the two tubes it was to connect (see Fig. 13.2). The jarring caused by the service
module segment falling back onto its support was able to dislodge the plastic insert,
in effect opening a hole in the discharge path, similar to a hole in a drinking straw.
However, there was no external evidence of this occurrence. The service module
was sent to Cape Kennedy for installation in the Apollo 13 vehicle.
Before launch the checkout procedure called for a filling of the oxygen tank
to ensure that it was in working condition. After the tank was confirmed to be
holding the liquid oxygen satisfactorily, it was to be detanked to await its final filling
before launch. However, when the detanking was attempted, no liquid could be
discharged through the fill tube by the application of pressure through the tank's
vent tube. Therefore, it was decided to use an alternate procedure of turning on a
heater within the tank and allowing it to evaporate the liquid oxygen. This was felt
safe to do because ofa thermal cutoff switch that would turn off the tank's internal
heater ifthe temperature were to rise too high. The heater was turned on and allowed
to heat the tank's interior over the following weekend. On Monday morning the
liquid had all been removed.
The oxygen supply to the fuel cells was designed to supply oxygen at about
6.9 MPa (1000 psi). This pressure would be maintained by the tank's internal heater,
and a uniform internal temperature would be ensured by a small fan within the tank.
This fan could be turned on to stir the fluid when the heater was operated. Thus,
with the operation of the heater and the fan, there would be a constant supply of
high-pressure oxygen. The 6.9-MPa (1000 psi) pressure is .above the critical
pressure of oxygen (see Table 1.1) so that no vaporization is involved in the
operation of the tank, and the density of the contained oxygen merely decreases as
.......
<::>
ilter
'... Sleeve
(Teflon)
L....J...L....JII Gauging Probe
(Aluminum)
Standpipe
n
=-
~
~
...
....
Fig. 13.2. Schematic of the oxygen tank that caused the explosion in Apollo 13. ...
Accidents: Prevention and Examples 211
the supply is used, with the maximum withdrawal of oxygen being reached when
the maximum allowed temperature is attained.
Subsequent testing of a similar thermal cutoff switch showed that the thermal
cutoff feature failed upon continued heating, allowing the heating current to persist
during the entire heating period over the weekend. The excessively high tempera-
ture attained was shown to bake the Teflon insulation on the heater and fan wiring
until it cracked and some pieces fell off. When the Apollo 13 was launched, placed
into the holding orbit, and then launched on the flight path to the moon, glitches in
the electrical system began to appear. Eventually, there was a pressure excursion
above the intended 6.9-MPa (1000 psi) level, and there was an explosion, blowing
off the cover of the service module where the oxygen tank was located. The
departure of the cover damaged one of the antennae and momentarily disrupted
communications with the ground. Also, the pressure in the oxygen tank decayed
rapidly to zero. Fortunately, the astronauts were rescued and returned to earth safely.
Subsequent investigation by an examining panel (including one of the authors,
FJE) showed that the electrical shorting had ignited the Teflon insulation, which
was shown to be capable of fairly rapid combustion in the high-pressure oxygen
atmosphere. Most of the combustion took place in the tube that served as the electric
wire feed-through into the Dewar's interior. The heating weakened the tube until it
ruptured, blowing off the top cap of the Dewar and causing the previously
mentioned occurrences and discharging the oxygen to the vacuum of space. This
analysis led to the conclusion that the main body of the tank was probably still
intact.
As the service module was jettisoned before reentry into the Earth's atmos-
phere, one of the astronauts was able to take a photograph of it as it floated off into
space. Unfortunately, the photograph was very seriously back-lighted by the sun,
and only a black area was visible where the tank was supposed to be. However, a
computer enhancement of the photograph was done, and the photograph then
showed that the tank was indeed there, and still intact.
Although such an accident might never have been thought possible because
so many anomalies were required to occur in sequence, this was a case where
several mishaps all occurred in series, leading to the accident. It should be pointed
out that the explanation of the accident might not have been possible were it not
for the excellent records that were kept by NASA. Another contributing factor was
the excellent support that was given to the analysis team in the way of performing
verification experiments when requested. In particular, this included the testing of
the duplicate thermal cutoff switch to show that it would fuse in the closed position,
the photographing of Teflon burning in high-pressure oxygen, and the computer
enhancing of the last photograph of the service module as it floated off into space.
The importance of record keeping cannot be overemphasized if one is to learn from
mishaps and prevent their recurrence.
212 Chapter 13
13.3. CONCLUSION
Notice that most of the accidents described in this chapter involve actions by
operating personnel that, in retrospect, seem inappropriate and stem from inade-
quate knowledge of the consequences of these actions. These accidents emphasize
the need for adequate and continued training.
REFERENCES
1. Knowlton, R E. (1981). Hazard and Operability Studies, Chemetics International Ltd., Vancouver,
Canada.
2. Ordin, P. M. (1974). Review of hydrogen accidents and incidents in NASA operations, in
Proceedings of the Ninth Intersociety Energy Conversion Engineering Conference, pp. 442-453,
American Society of Mechanical Engineering, New York.
3. Reider, R, Otway, H. J., and Knight, H. T. (1965). An unconfined, large-volume hydrogen/air
explosion, Pyrodynamics 2, 249.
4. Scott, L. E. (1964). Neck plug experiments in liquid-helium shipment, in Advances in Cryogenic
Engineering (K. D. Timmerhaus, ed.), Vol. 9, pp. 379-389, Plenum Press, New York.
5. Van Wylen, G. J., and Sonntag, R E. (1986). Fundamentals of Classical Thermodynamics, John
Wiley & Sons, New York.
Appendix A
A listing of the elements of the Code of Federal regulations that are pertinent to the
handling of cryogenic fluids is given in Table 11.12. Further details of these
elements are presented in this Appendix. Table A.l gives additional details of some
of the regulations pertaining to liquefied natural gas facilities. Table A.2 presents a
similar listing for cryogenic liquid tank car tanks, and Table A.3 gives further details
of OSHA regulations for the handling of cryogenic liquids in the work place.
Table A.I. Liquefied Natural Gas Facilities: Federal Safety Standards (49 CFR Part 193)
SubpartA--{Ieneral
Section 193.1 Scope of part
193.3 Applicability
193.5 Definitions
193.7 Rules of regulatory construction
193.9 Filing inspection and maintenance plans
193.11 Incorporation by reference
Subpart B-Site Related Design Requirements
Section 193.101 Scope
193.\03 Acceptable site
193.107 Thermal radiation protection
193.109 Combustible vapor-gas dispersion protection
193.111 Seismic investigation and design
193.113 Flooding
193.115 Soil characteristics
193.117 Wind forces
193.119 Other severe weather and natural conditions
193.121 Adjacent activities
193.123 Separation of components
Subpart C-Materials
Section 193.201 Scope
193.203 General
193.205 Extreme temperatures; normal operations
213
214 Appendix A
193.1139 Purging
193.1141 Operating records
Subpart ~Maintenance
Section 193.1201 Scope
193.1203 General
193.1205 Maintenance procedures
193.1207 Maintenance of fire fighting equipment
193.1209 Isolating and purging
193.1211 Testing repairs
193.1213 Contaminants
193.1215 Testing control systems
193.1217 Testing transfer hoses
193.1219 Inspecting storage tanks
193.1221 Maintenance records
Subpart N-Fire Prevention
Section 193.1301 Scope
193.1303 General
193.1305 Fire prevention plan
193.1307 Fire fighting plan
193.1309 Coordination with public safety agencies
193.1311 Training
193.1313 Records
Subpart O-Corrosion Control
Section 193.1401 Scope
193.1403 General
193.1405 Corrosion control overview
193.1407 Atmospheric corrosion control
193.1409 External corrosion control; buried or submerged components
193.1411 Internal corrosion
193.1413 Environmentally induced cracking
193.1415 Interference currents
193.1417 Contaminants
193.1419 Monitoring corrosion control
193.1421 Remedial measures
193.1423 Corrosion control records
Appendix A
I. List of Organization and Addresses
II. Documents Incorporated by Reference
Table A.2. General Specifications for Cryogenic Liquid Tank Car Tanks: 49 CFR 179
Subpart F-Specifications for Cryogenic Liquid Tank Car Tanks and Seamless Steel
Tanks (1994 Edition)
Section 179.400 General specifications applicable to cryogenic liquid tank car tanks
179.400-1 General
179.400-2 Approval
179.400-3 Type
179.400-4 Insulation system and performance standard
218 Appendix A
179.400-5 Materials
179.400-6 Bursting and buckling pressure
179.400-7 Tank heads
179.400-8 Thickness of plates
179.400-9 Stiffening rings
179.400-10 Sump or siphon bowl
179.400-11 Welding
179.400-12 Post weld heat treatment
179.400-13 Support system for inner tank
179.400-14 Cleaning of inner tank
179.400-15 Radioscopy
179.400-16 Access to inner tank
179.400-17 Inner tank piping
179.400-18 Test of inner tank
179.400-19 Valves and gages
179.400-20 Pressure relief devices
179.400-21 Test of pressure relief valves
179.400-22 Protective housings
179.400-23 Operating instructions
179.400-24 Stamping
179.400-25 Stenciling
179.400-26 Certificate of construction
Section 179.40 I Individual specification requirements for cryogenic liquid tank car tanks
Table A.3. Outline of OSHA Regulation for Flammable and Combustible Liquids
[Occupational Safety and Health Administration, Labor; 29 CFR Ch. XVII
(7-1-93 Edition)
(ii) Fabrication
(A) Reserved
(B) Metal tank fabrication
(iii) Atmospheric tanks
(A) Design and fabrication standards
(I) Underwriters' Laboratories, Inc. No. 142; No. 58; or No. 80
(2) American Petroleum Institute No. 12A or No. 650
(3) American Petroleum Institute No. 12B; No. 12D; or No. 12F
(B) Above-ground use of tanks designed for underground use
(C) Atmospheric tank use oflow-pressure tanks and pressure vessels
(D) Use with flammable or combustible liquid at or above its boiling point
(iv) Low-pressure tanks
(A) Normal operating pressure
(B) Design and fabrication standards
(I) American Petroleum Institute No. 620
(2) ASME Boiler and Pressure Vessel Code
(C) Limits for use of tanks built according to Underwriter's Laboratories standards
(D) Use of pressure vessels for low-pressure tanks
(v) Pressure vessels
(A) Normal operating pressure
(B) Design and fabrication according to ASME Boiler and Pressure Vessel Code
(vi) Provisions for internal corrosion
(2) Installation of outside aboveground tanks
(i) Reserved
(ii) Spacing (shell-to-shell) between aboveground tanks
(A) Separation distance
(B) Separation distance exceptions
(C) Crude petroleum in conjunction with production facilities
(0) Separation distance for unstable flammable or combustible liquids
(E) Tank spacing for compacted three or more rows or for irregular pattern
(F) Spacing for an LPG container and a flammable or combustible liquid
storage tank
(iii) Reserved
(iv) Normal venting for aboveground tanks
(A) Atmospheric storage tank vent
(B) Sizing of normal vents
(C) Venting provisions to prevent pressure or vacuum as a result of filling or
emptying
(D) Venting provisions for multiple fiU or withdrawal connections
(E) Vent location for ignitable vapors
(F) Normally closed vents
(G) Flame arresters
(v) Emergency relief venting for fire exposure for aboveground tanks
(A) Pressure relief of excessive pressure caused by exposure fire
(B) Pressure relieving construction for a vertical tank
(C) Total venting capacity
(0) Total rate of venting determination
(E) Total emergency relief venting capacity determination
(F) Required airflow rate determination
(G) Outlet of vents and vent drains
Code of Federal Regulations 221
(ii)Exceptions
(A) Oil or gas well connections
(B) Engines
(C) Piping per pressure vessel code
(iii) Definitions
(2) Materials for piping, valves, and fittings
(i) Required materials
(ii) Exceptions
(iii) Linings
(iv) Low-melting materials
(3) Pipe joints
(4) Supports
(5) Protection against corrosion
(6) Valves
(7) Testing
(k) Marine service stations
(I) Dispensing
(i) Dispensing area location
(ii) Dispensing units
(iii) Dispensing nozzles
(2) Tanks and pumps
(i) Location of tanks and pumps non-integral to dispensing unit
(ii) Alternative location provisions
(iii) Shore tank location
(iv) Tank outlet location
(3) Piping
(i) Piping between shore tanks and dispensing units
(ii) Shut off valve
(iii) Protection from physical damage
(iv) Grounding
(4) Definition; as used in this section
List of Symbols
Does not include symbols used to denote units, e.g., K for Kelvin.
A Flow area of relief valve
B Parameter defined by Eq. (4.3)
C Expansion factor for flow through relief valve
Ce Capacitance
Cp Specific heat at constant pressure
Cv Specific heat at constant volume
D Diameter of pipe
Di Inside diameter
Do Outside diameter
d Duration of a fire
E Elastic (or Young's) modulus
f Frequency of oscillations
G Mass flux [kg/(sm2)]
Gs Gas mass flow for Baker plot [lbm/(ft2hr)]
gc Unit conversion factor (see Chapter 5)
H Height of a "U" bend in a pipeline (Fig. 4.5)
I Electrical current
K Discharge coefficient for flow through relief valve
k Rate constant for conversion of orthohydrogen to parahydrogen
L Inductance of coil, or length
Ls Liquid mass flow for Baker plot [lbm/(ft2hr)]
LG Length of cryogenic transfer line filled with gas during cool-down
LL Length of cryogenic transfer line filled with liquid during cool-down
Lo Length of a specimen at 0 K
Lp Length of a pipeline containing a "U" bend (Fig. 4.5)
LT Length of a specimen at temperature T; e.g., L300 = length at 300 K
M,MW Molecular weight
m Total mass flow (Ls + GB)
mf Flow rate (kg/s)
225
226 Appendix B
List of Acronyms
229
230 Appendix C
231
232 Index