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Safetygram #7

Liquid Nitrogen

General inner vessel. Vaporizers convert the liquid nitrogen


to its gaseous state. A pressure control manifold
Liquid nitrogen is inert, colorless, odorless, non- controls the pressure at which the gas is fed to
corrosive, nonflammable, and extremely cold. the process. Processes that use nitrogen as a
Nitrogen makes up the major portion of the atmo- liquid do not require the vaporizers and pressure
sphere (78.03% by volume, 75.5% by weight). control manifold.
Nitrogen is inert and will not support combustion;
however, it is not life supporting. Physical and chemical properties are listed
in Table 1.
Nitrogen is inert except when heated to very high
temperatures where it combines with some of the Manufacture
more active metals, such as lithium and magne-
sium, to form nitrides. It will also combine with Nitrogen is produced at air separation plants by
oxygen to form oxides of nitrogen and, when com- liquefaction of atmospheric air and separation of
bined with hydrogen in the presence of catalysts, the nitrogen by continuous cryogenic distillation.
will form ammonia. The nitrogen is then recovered as a cryogenic
liquid.
Since nitrogen is noncorrosive, special materials
of construction are not required to prevent corro- Uses
sion. However, materials of construction must be
Nitrogen is the largest volume inorganic chemical
selected to withstand the low temperature of liquid
sold in the world, supporting a multitude of com-
nitrogen. Vessels and piping should be designed to
mercial and technical applications. In its liquid
American Society of Mechanical Engineers (ASME)
state, nitrogen is used for food freezing, plastic
specifications or the Department of Transportation
and rubber deflashing and grinding, cooling, metal
(DOT) codes for the pressures and temperatures
treating, biological sample preservation, pulveriza-
involved.
tion, and other temperature-related applications.
Although used more commonly in the gaseous
state, nitrogen is commonly stored and transported Health Effects
as a liquid, affording a more cost-effective way of
Being odorless, colorless, tasteless, and nonirritat-
providing product supply.
ing, nitrogen has no warning properties. Humans
When nitrogen is converted to liquid form it possess no senses that can detect the presence
becomes a cryogenic liquid. Cryogenic liquids are of nitrogen. Although nitrogen is nontoxic and
liquefied gases that have a normal boiling point inert, it can act as a simple asphyxiant by displac-
below –238°F (–150°C). Liquid nitrogen has a ing the oxygen in air to levels below that required
boiling point of –320.5°F (–195.8°C). The tem- to support life. Inhalation of nitrogen in excessive
perature difference between the product and the amounts can cause dizziness, nausea, vomiting,
surrounding environment, even in winter, is sub- loss of consciousness, and death. Death may
stantial. Keeping this surrounding heat from the result from errors in judgment, confusion, or loss
product requires special equipment to store and of consciousness that prevents self-rescue. At
handle cryogenic liquids. low oxygen concentrations, unconsciousness and
death may occur in seconds and without warning.
A typical system consists of the following com-
ponents: a cryogenic storage tank, one or more Personnel, including rescue workers, should
vaporizers, a pressure and temperature control not enter areas where the oxygen concentra-
system. The cryogenic tank is constructed like, in tion is below 19.5%, unless provided with a
principle, a vacuum bottle. It is designed to keep self-contained breathing apparatus or air-line
heat away from the liquid that is contained in the respirator.
For more information on oxygen-deficient atmo- Table 1
spheres, consult Air Products’ Safetygram #17,
“Dangers of Oxygen-Deficient Atmospheres.” Liquid Nitrogen Physical and Chemical Properties

Extensive tissue damage or burns can result Chemical Formula N2


from exposure to liquid nitrogen or cold nitrogen
Molecular Weight 28.01
vapors.
Boiling Point @ 1 atm –320.5°F (–195.8°C)
Containers
Freezing Point @ 1 atm –346.0°F (–210.0°C)
Liquid nitrogen is stored, shipped and handled
Critical Temperature –232.5°F (–146.9°C)
in several types of containers, depending upon
the quantity required by the user. The types of Critical Pressure 492.3 psia (33.5 atm)
containers in use are the dewar, cryogenic liquid
cylinder, and cryogenic storage tank. Storage Density, Liquid @ BP, 1 atm 50.45 lb/scf
quantities vary from a few liters to many thou- Density, Gas @ 68°F (20°C), 1 atm 0.0725 lb/scf
sands of gallons. Since heat leak is always pres-
ent, vaporization takes place continuously. Rates Specific Gravity, Gas (air=1) @ 68°F (20°C), 1 atm 0.967
of vaporization vary, depending on the design of
Specific Gravity, Liquid (water=1) @ 68°F (20°C), 1 atm 0.808
the container and the volume of stored product.
Specific Volume @ 68°F (20°C), 1 atm 13.80 scf/lb
Containers are designed and manufactured
according to the applicable codes and Latent Heat of Vaporization 2,399 Btu/lb mole
specifications for the temperatures and pressures
Expansion Ratio, Liquid to Gas, BP to 68°F (20°C 1 to 694
involved.

Figure 1 protect the cylinders from pressure buildup. These Figure 2a


containers operate at pressures up to 350 psig
A Typical Dewar Typical Cryogenic Liquid Cylinder,
and have capacities between 80 and 450 liters of
side view
liquid. Liquid Level
Gauge

Product may be withdrawn as a gas by passing Handling Ring


Handling Post
liquid through an internal vaporizer or as a liquid
Annular Space
under its own vapor pressure. For more details on Rupture Disk
the construction and operation of cryogenic liquid Inner Vessel Vent Tube
Gas Use Liquid Tube
cylinders, consult Air Products’ Safetygram #27, Vaporizer Float Assembly
“Cryogenic Liquid Containers.” (Optional)
Outer Vessel
Rubber Shock
Cryogenic Storage Tanks Mounts
A typical customer installation (see Figure 3) Foot Ring
includes a tank, a vaporizer, and a pressure control
manifold. Tanks may be spherical or cylindrical
Dewars in shape. They are mounted in fixed locations as Figure 2b
Figure 1 illustrates a typical, vacuum-jacketed stationary vessels or on railroad car or truck chas-
dewar. A loose fitting dust cap over the outlet of sis for easy transportation. Sizes range from 500 Typical Cryogenic Liquid Cylinder,
top view
the neck tubes prevents atmospheric moisture to 420,000 gallons and all tanks are powder- and
Vent Pressure Rupture Vent Relief Pressure Rupture
from plugging the neck and allows gas produced vacuum-insulated in the annular space. Tanks are Valve Gauge Disk Valve Valve Gauge Disk
from vaporized liquid to escape. This type of con- equipped with various circuits to control product
tainer is a nonpressurized container. The unit of fill, pressure buildup, pressure relief, product
measure for the capacity of a dewar is typically withdrawal, and tank vacuum. Tanks are designed
the liter. Five to 200 liter dewars are available. to ASME specifications for the pressures and tem-
Product may be removed from small dewars by peratures involved.
pouring, while larger sizes will require a transfer
tube. Cryogenic liquid cylinders that are pressur- Transfer Lines Pressure
Liquid Pressure Building Building Economizer Liquid Gas
ized vessels are sometimes incorrectly referred to A liquid transfer line is used to safely remove liquid Valve Regulator Valve Regulator Valve Disk

as dewars. product from dewars or cryogenic liquid cylinders.


A typical transfer line for dewars is connected to Liquid product is typically removed through
Cryogenic Liquid Cylinders a bayonet that provides a means of using product insulated withdrawal lines to minimize the loss
Figure 2 shows a typical cryogenic liquid cylinder. vapor pressure buildup or an external pressure of liquid product to gas. Insulated flexible or rigid
Cryogenic liquid cylinders are insulated, vacuum- source to remove the liquid. For cryogenic liquid lines are used to withdraw product from storage
jacketed pressure vessels. They come equipped cylinders, the transfer line is connected to the tanks. Connections on the lines and tanks vary by
with safety relief valves and rupture discs to cylinder’s liquid withdrawal valve. manufacturer.
Use only transfer lines and equipment designed for
Figure 3 Figure 4
use with cryogenic liquids. Some elastomers and
A Typical Customer Station with a Nonflammable Gas Shipping Label metals, such as carbon steel, may become brittle at
Cryogenic Storage Tank extremely low temperatures and may easily frac-
ture. These materials must be avoided in cryogenic
service.

On gas withdrawal systems use check valves or


other protective apparatus to prevent reverse flow
into the container.On liquid systems pressure relief
devices must be used in lines where there is the
potential to trap liquid between valves. It is recom-
mended that all vents be piped to the exterior of the
building.

Liquid containers should not be left open to the


atmosphere for extended periods. Keep all valves
closed and outlet caps in place when not in use. If
NOTE: Liquid cylinders designed to dispense If oxygen-deficient atmospheres are suspected or restriction results from freezing moisture or foreign
gaseous nitrogen have valves equipped with can occur, use oxygen monitoring equipment to test material present in openings and vents contact the
standard Compressed Gas Association (CGA) for oxygen-deficient atmospheres. Review the liquid vendor for instructions. Restrictions and blockages
outlets. Suitable pressure regulating equipment nitrogen Material Safety Data Sheet (MSDS). may result in damgerous over-pressurization. Do not
may be attached. Valves provided for the with- attempt to remove the restriction without proper in-
drawal of liquid product are also equipped with Buildings structions. If possible move the cylinder to a remote
standard CGA outlets, but are different than the location.
connections used for gaseous withdrawal. This Because of the large expansion ratio of liquid to gas,
is to prevent cross connections between pro- it is very important to provide adequate ventilation For additional information on the storage and
cesses using liquid or gaseous product. in areas using liquid nitrogen. A minimum of six air handling of cryogenic liquids refer to Air Products’
changes per hour are suggested in these areas. Safetygram-16, “Safe Handling of Cryogenic
Shipment of Liquid Nitrogen Liquids”, and CGA Pamphlet P-12, “The Safe
Provide monitoring for areas where oxygen dis-
Handling of Cryogenic Liquids”.
Containers used for transporting liquid nitrogen placement may occur.
at less than 25 psig (40 psia) pressure are Personal Protective Equipment
OSHA has established 19.5% oxygen concentration
UN/DOT authorized containers. These are contain-
as the minimum for working without supplied air. (PPE)
ers built to other than DOT specifications but are
authorized by the DOT for use in the transport of Remember, nitrogen has no warning properties! Personnel must be thoroughly familiar with proper-
approved products. Containers used for transport- ties and safety considerations before being allowed
ing liquid nitrogen at pressures greater than 25 Storage and Handling to handle liquid nitrogen and/or its associated
psig (40 psia) need to be designed, manufactured, equipment.
and tested to DOT specifications. Store and use liquid containers with adequate venti-
lation. Do not store containers in a confined area or Eyes are most sensitive to the extreme cold of liquid
For air shipments, all packages must be in compli- in area unprotected from the extremes of weather. nitrogen and its vapors. The recommended personal
ance with International Air Transport Association/ Cryogenic containers are equipped with pressure protective equipment when handling or using liquid
International Civil Air Organization (IATA/ICAO) relief devices designed to control the internal pres- nitrogen is a full faceshield over safety glasses;
Dangerous Goods Regulations, as well as DOT sure. Under normal conditions these containers will loose-fitting thermal insulated or leather gloves; and
regulations. periodically vent product. Do not plug, remove or long-sleeved shirts and pants without cuffs, espe-
tamper with any pressure relief device. cially whenever the possibility of exposure or a spill
DOT Hazard Class: 2.2 exists. In addition, safety shoes are recommended
Cryogenic containers must be stored, handled and for those involved with the handling of liquid nitro-
DOT Shipping Label: Nonflammable Gas (Fig. 4)
transported in the upright position. When moving gen containers.
except none for cargo tanks under 23 psig
never tip, slide or roll containers on their side. Use
Identification Number: UN1977 a suitable hand truck for moving smaller contain- In emergency situations, self-contained breathing
DOT Shipping Name: Nitrogen, Refrigerated Liquid, ers. Move larger containers by pushing, not pulling. apparatus (SCBA) must be used.
2.2, UN1977 Avoid mechanical and thermal shock. Never allow
any unprotected part of the body to come in contact First Aid
Safety Considerations with uninsulated pipes or equipment containing
cryogenic product. The extreme cold will cause flesh People suffering from lack of oxygen should be
The hazards associated with liquid nitrogen are to stick fast and potentially tear on withdrawal. moved to fresh air. If the victim is not breathing,
exposure to cold temperatures, which can cause administer artificial respiration. If breathing is dif-
severe burns; overpressurization due to expansion If there is any difficulty in operating the container ficult, administer oxygen. Obtain immediate medical
of small amounts of liquid into large volumes of gas valve or container connections discontinue use and attention.
in inadequately vented equipment; and asphyxi- contact the vendor. Do not remove or interchange
ation due to displacement of oxygen in the air in connections. Use only the properly assigned con-
confined work areas. nections. Do not use adaptors.
Self-contained breathing apparatus (SCBA) In the case of massive exposure, remove clothing
may be required to prevent asphyxiation of while showering the victim with warm water. Call
rescue personnel. a physician immediately.

For skin contact with cryogenic liquid nitrogen, If the eyes are exposed to the extreme cold of the
remove any clothing that may restrict circulation liquid nitrogen or its vapors, immediately warm
to the frozen area. Do not rub frozen parts, as the frostbite area with warm water not exceeding
tissue damage may result. As soon as practical, 105°F (40°C) and seek immediate medical
place the affected area in a warm water bath that attention.
has a temperature not in excess of 105°F (40°C).
Never use dry heat. Fire Fighting
Frozen tissue is painless and appears waxy with Since nitrogen is nonflammable, special fire fight-
a possible yellow color. It will become swollen, ing equipment and instructions are not needed. As
painful, and prone to infection when thawed. If the a note of caution, however, water streams must
frozen part of the body has been thawed, cover not be directed toward venting nitrogen, as the
the area with a dry sterile dressing with a large water will freeze and plug the pressure relief vent
bulky protective covering, pending medical care. and may result in a container failure.

Emergency Response System Product Safety Information


The accuracy or completeness of all statements,
technical information and recommendations • Call: +1-800-523-9374 • For MSDS, Safetygrams,
contained herein is not guaranteed and no war- (Continental U.S. and Puerto Rico) and Product Safety Information
ranty of any kind is made in respect thereto. www.airproducts.com/productsafety
Such statements and information are given for • Call: +1-610-481-7711 (other locations)
general use only and should not be solely relied • 24 hours a day, 7 days a week
upon by the recipient when establishing appro-
priate procedures for his or her own operation. • For assistance involving Air Products and
Chemicals, Inc. products

Technical Information Center Information Sources


• Call: +1-800-752-1597 (U.S.) • Compressed Gas Association (CGA)
www.cganet.com
• Call: +1-610-481-8565 (other locations)
• American Chemistry Council
• Monday–Friday, 8:00 a.m.–5:00 p.m. EST www.americanchemistry.com
• Fax: +1-610-481-8690
• E-mail: gastech@airproducts.com

For More Information


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