STORAGE:
Acrylonitrile is commonly delivered to storage in bulk by truck, rail car, pipeline, barge or ship.
It is also delivered in drums. When designing a storage facility consider the optimum storage
capacity keeping in mind the expected delivery vehicle and quantity, and estimated future
capacity requirements. Avoid storage times in excess of six months to minimize the potential for
degradation of Acrylonitrile quality. See prevention of polymerization (below) for
maintenance of polymerization inhibitors during long-term storage.
Prevention of Polymerization
A useful means of preventing unwanted polymerization in storage is to confirm that product
specifications are met. Product specifications insure that substances which can initiate polymerization are
not present in dangerous amounts. Acrylonitrile is incompatible with a variety of chemicals and
conditions which can lead to violent reactions, usually initiation of rapid exothermic polymerization.
Although extremely pure Acrylonitrile is stable at temperatures of 100C or more, in the presence of even
trace amounts of these incompatible materials polymerization can be rapid and unpredictable. These
chemicals and conditions are shown in Table 3.1.
The potential for unwanted polymerization is minimized by the inhibitor system: water (0.2 to 0.5
weight percent) and MEHQ (35 to 45 ppm) (see Section 2.) Each compound interrupts potential
polymerization reactions by consuming trace reactive intermediates before polymerization begins or
becomes uncontrolled. Water inhibits ionic polymerization by trapping basic or acidic intermediates.
MEHQ inhibits free radical polymerization by trapping free radical intermediates. MEHQ requires
dissolved oxygen for proper inhibition of polymerization. Under most conditions, Acrylonitrile will
contain sufficient quantities of dissolved oxygen from exposure to air during manufacturing, handling and
storage.
Prevention of Flammability
Nitrogen blanketing substantially reduces the potential for flammability of vapors above the surface of
liquid Acrylonitrile. During nitrogen blanketing, oxygen is purged from the vapor space in the vessel or
tank. The oxygen level should be purged to below 8 percent. Although the MEHQ and water inhibitor
system will remain effective well below 8 persent oxygen in the vapor space, complete exclusion of
oxygen is discouraged because the inhibitor system becomes ineffective when oxygen is absent. Nitrogen
blanketing may be accomplished through various systems.
Maintaining Stability in Storage
The most important first step in safe handling and storing of Acrylonitrile is to follow good storage
practices. Uninhibited Acrylonitrile should never be stored or transported, and Acrylonitrile should be
inhibited with the proper levels of water and MEHQ (see above). Exposure to the chemicals and
conditions known to be incompatible with Acrylonitrile (see Table 3.1) should be scrupulously avoided.
Sources of heat should also be avoided, including pumping Acrylonitrile against a closed valve to
unusually high pressures or for unusually long periods of time. Storage of Acrylonitrile should be limited
to less than 6 months. Acrylonitrile should be monitored for a series of indications that unwanted
polymerization may be occurring. Haziness in a sample of stored Acrylonitrile can indicate formation of
poly (acrylonitrile), which is insoluble in the monomer. The pH, measured as a 5 percent aqueous solution
by weight, should be watched. If the pH is in the basic range (above pH 7.3) ionic polymerization may be
occurring, and this polymerization can be accompanied by the generation of ammonia. The MEHQ
inhibitor level should be monitored to assure that inhibitor is not being consumed. Finally, a temperature
rise in the monomer can indicate unwanted reaction.
If any of the above conditions is observed, the following
steps should be taken IMMEDIATELY:
1. If the pH of a 5 percent aqueous solution of Acrylonitrile is above 7.5, the Acrylonitrile should be
acidified. It has been recommended to acidify by adding a 1:2 aceticacid: Acrylonitrile mixture and
mixing thoroughly.
2. A 4 percent solution of hydroquinone, HQ, in Acrylonitrile should be added with thorough mixing to
bring the HQ concentration to about 100 ppm. HQ, while it discolors Acrylonitrile readily, is reported to
be a more effective inhibitor than MEHQ.
3. Water can be added to inhibit ionic polymerization and to dilute the Acrylonitrile monomer.
4. External cooling may be accomplished by spraying water on the container or tank. However, this may
not be effective if the container is insulated.
5. Pressure buildup can be alleviated by venting the tank through an adequate pressure relief-vent system.
Assure that Acrylonitrile is efficiently condensed and that the condensed Acrylonitrile is properly
inhibited.
Tank Location
The arrangement of tanks and equipment should take into account access for normal operation
and maintenance, emergency response teams and equipment, as well as emergency evacuation. Storage
facility personnel should also be familiar with locally available fire fighting capabilities.
Tank farms housing other chemicals must be designed to keep all chemicals segregated especially in
the event of a spill or fire. Products (Bromine Ammonia Amines Copper and copper alloys Strong Acids Strong
bases (e.g. potassium hydroxide, sodium hydroxide Peroxides or other free radical initiators)which chemically
react with Acrylonitrile should not be stored in the vicinity. Storage tanks should be constructed at ground
level and in open air. This placement will allow easy detection of unwanted vapor emissions and will aid
natural ventilation in dispersing vapors.
Tanks must be located away from a potential source of ignition, including the possibility of
radiation from a fire in an adjacent area. Consult local regulations to determine and design adequate space
between tanks.
In the U.S. all tanks should be surrounded by a dike wall capable of containing 110 percent of the
largest tank within the dike. The walls and floor of the dike should be impervious to liquid and designed
to withstand a full hydrostatic head. Suitable construction materials include compacted clay, concrete,
synthetic sheeting, or geotextiles. In many locations around the world, selection of these material may
be subject to applicable regulatory requirements. Dike walls should not be higher than 5 feet in order to
insure adequate ventilation of the area, ready access for fire fighting, and easy escape during an
emergency. Intermediate dike walls are recommended to segregate tanks into groups and to minimize the
impact of an accidental spill on adjacent areas.
Tank Design
The tank should be designed in accordance with an appropriate, recognized standard of good
engineering. Stainless steel or carbon steel are recommended for tank construction.
Carbon steel tanks are usually cleaned either by chemical or physical means before initial use to
remove rust. If the tank is cleaned by chemical means, further cleaning with water, according to an
accepted procedure, is mandatory in order to prevent a potential chemical reaction. Copper materials
should not be used in the construction of an Acrylonitrile storage tank. Copper can induce polymerization
and also discolor Acrylonitrile. Tank roofs should be fixed, with or without an internal floating roof.
Internal floating roofs significantly reduce vapor emissions. These roofs may be constructed of aluminum
for weight savings and lower expense. Seals on internal floating roofs may be vapor or liquid mounted
double seal. Manufacturers specifications should be consulted for the proper type of seal to
accommodate individual storage locations and climatic conditions.
Piping
A tank discharge line should be provided which should be a minimum of 2 nominal bore. The line may
be taken from the bottom or side of the tank and should be fitted with an isolating valve, as close to the
tank wall as possible. In all cases, discharge should be by pump. Capability for draining the tank should
be provided. Drainage should take place from the lowest point in the tank with a suitable isolation valve.
The isolation valve should be closed and locked when not in use. Wherever possible, continuous welding
should be used in pipeline construction. Flange joints should be used where pipes are periodically
disconnected for maintenance or inspection.
Flanges should conform to the American National Standards Institute (ANSI) 150 lb. PTFE envelope
gaskets should be used; gaskets of similar non-swelling material are also suitable. Screwed fittings should
not be used except with stainless steel components.
Piping should not be located over doorways or windows, or close to possible sources of ignition to
minimize the possibility of accidental damage.
Pumps
Pumps should be located outside of tank dikes, on an impervious base, in open space. They should not be
located in walled-off or confined spaces. Centrifugal pumps designed to ANSI (American National
Standards Institute) standards or an equivalent are normally used for transferring Acrylonitrile to and
from storage.
The pump mechanical seals can be of either the single, double or tandem seal design. To maintain
product quality, both the single and double seals should be self flushing. For added environmental
protection, tandem seals with a self flush inboard and a seal water flush outboard seal may be used. Seal
face materials should be carbon against silicon carbide or carbon against tungsten carbide. For
Acrylonitrile service, the seal gasket elastomer should be silicone rubber.
Plastic pumps should not be used. Pumps should be constructed of either cast steel or stainless
steel. Pumps may be driven pneumatically, hydraulically or electrically. Electric pumps should be
flameproof. Remote control pumps should also have a shut-off button at the pumps delivery point.
Pumping output should not exceed the recommended speed or capacity of the piping system, especially in
the discharge pipelines. Gravitational flow may occur in a centrifugal pump when the pump is stopped.
This flow should be anticipated and compensated for.
Valves
Isolating valves may be ball or gate valves with PTFE seats. Angle or globe valves are also acceptable on
Acrylonitrile service. Diaphragm valves should not be used with Acrylonitrile. Valve bonnet gaskets may
be soft iron, spiral wound or equivalent. Valve stem packings should be Garlock 9000 EVSP (or
equivalent) graphite packing.
Nitrogen Blanketing
Nitrogen blanketing is recommended for keeping the oxygen level at or below 8 percent, for fire
protection.
Vapor Control System
A vapor control system should be installed at the facility to control displaced vapors from
transport equipment during loading or unloading. Vapors should be kept from release
into the atmosphere for the protection of operators and the environment.
A number of different control systems are available and local regulatory requirements may vary.
Vapors can be destroyed through incineration; recovered through a refrigeration/condensation process;
absorbed through charcoal; processed through a scrubbing system; or vapor balanced to a storage tank.
Proper training of ship or barge and facility personnel is essential for safe operation. Training is essential
to reduce the possibility of the following hazards: flame propagation from vessel to shore systems; over or
under pressurization; and chemical spillage.
Electrical Considerations
Pumps, tanks, electric motors and all parts of the system must be effectively grounded to prevent
the accumulation of static electrical charges. Working areas, for example, tank stairs, platforms, loading
and unloading points, should be adequately illuminated during working hours.
Electrical equipment used in hazardous areas must be non-sparking or otherwise suitable for the
area where it will be used. The selection, installation and maintenance of such electrical equipment should
be based on aninternationally-accepted hazardous area classification
scheme. First, determine the areas classification. Next, consult an accepted electric code which lists
suitable equipment for use in that area classification.
For instance, the following selection scheme is used in the United States. The appropriate national
or international electric code should be used in conjunction with the area classification
methodology for a heavier-than-air gas source. See Appendix 3.1 for API (American Petroleum
Institute)Recommended Practice 500 diagrams of tank, rail/truck, and marine area classifications. The
National Electric Code is not provided and must be consulted elsewhere.
Transfer and Transport
Equipment and procedures for transfer and transport of Acrylonitrile will vary widely depending on
prevailing national and local operating regulations. However, some basic principles of safe handling
apply regardless of a facilitys location.
General Safety for Transfer and Transport
Acrylonitrile is commonly transported via ISO tank container, bulk truck, rail car, drum, barge or ship.
Product transfer facilities and transport equipment must be designed to eliminate or responsibly manage
potential Acrylonitrile handling hazards. Facilities and equipment must be diligently maintained and
properly used. Transport equipment should meet the requirements of state, federal and international
regulations and may be subject to periodic inspection and testing under those regulations. Recognized
authorities may perform inspections and testing in the facilitys region. Written operating instructions
should be available at all transfer points, covering the applicable procedures forAcrylonitrile transfer.
Personnel at all filling points must be fully trained in the implementation of the instructions.
Both routine and emergency transfer situations should be covered in the written instructions.
An inspection check list is recommended for evaluating the condition of Acrylonitrile transport
equipment. The evaluation should be performed before, during and after transfer. All necessary protective
clothing and emergency equipment should be readily available at all key areas of the transfer operation.
Personnel should be thoroughly trained in the use of this clothing and equipment. (See Section 6)
Static electricity may build up during the loading or unloading of any Acrylonitrile transport mode. An
approved grounding connection should be used during loading and unloading, and the grounding system
should be checked periodically.
Nitrogen blanketing substantially reduces the potential for flammability of vapors above the
surface of liquid Acrylonitrile. Nitrogen blanketing is used in closed cargo transfer handling systems
during loading and unloading of truck, rail car or marine transport equipment. See Section 3 for further
explanation of nitrogen blanketing.
Fire Safety
Fire-Related Chemical Properties
Acrylonitrile is a flammable liquid requiring safe handling to avoid fire or explosion. The chemical must
not contact an open flame. At room temperature, Acrylonitrile vapors combined with air form flammable
or explosive mixtures. See Table 5.1 for Acrylonitrile flammability values. Acrylonitrile vapors are
heavier than air and may travel considerable distances or settle in low-lying areas. Acrylonitrile vapors
may explode in the presence of a source of ignition. Ignited vapors also have the potential to flash back
to the origin of the vapor, creating another fire hazard at the source.
Prevention
The most effective way of preventing an Acrylonitrile fire is to keep Acrylonitrile vapors contained or
keep them from a source of ignition. Vapor emissions should be controlled, and monitoring for accidental
vapor releases should be performed to guard against possible ignition. In addition to open flames, other
sources of ignition (electricity, static, etc.) should be eliminated in areas generating unavoidable
vapors, or where accidental vapor releases are highly probable. All mechanical equipment used near
Acrylonitrile storage and handling areas must be designed for low flammability (i.e., intrinsically safe).
Also, fire fighting equipment, sufficient for the maximum incident potential, should be readily at hand in
these areas.
Extinguishment
Acrylonitrile fires may be extinguished with:
Foam AFFF - (aqueous film forming foam) that is alcohol resistant is recommended for extinguishing
polar solvents such as Acrylonitrile. Protein and other foams may be
ineffective.
Dry chemical - potassium bicarbonate-based dry chemical
Carbon dioxide/Halon - substitute
Water alone is ineffective as an extinguishing agent, however, it may be used to cool fire-exposed
containers, to disperse vapors, to protect personnel or to flush spill away from sources of ignition.
Exposed firefighters should wear approved self-contained breathing apparatus with full face mask in the
positive pressure mode, and full protective equipment. For advanced or massive fire, fire fighting should
be done from a safe distance or protected location. Care must be exercised in determining sufficient fire
fighting ability when confronting an incident. The potential for a small fire to increase rapidly into a
major fire should be anticipated. A single fire fighter should immediately notify other emergency
response personnel who will be ready to assist if the fire increases.
Decomposition Products
Burning Acrylonitrile may produce toxic gases such as hydrogen cyanide, nitrogen dioxide or carbon
monoxide. Emergency response personnel, as well as the surrounding population, must be protected
against exposure to these gases. Evacuation procedures should be in place in all work
and public areas adjacent to Acrylonitrile storage and handling facilities. Run-off from fighting an
Acrylonitrile fire should be contained to prevent harm to the surrounding public and environment.
HEALTH and SAFETY
Circumstances Requiring Respirator Use
See Table 6.3 - Acrylonitrile respiratory protection for recommended respirator types at varying exposure
levels. Respiratory protection should be used in the following
circumstances:
during the installation of engineering controls
during maintenance and repair activities
during reactor cleaning where use of engineering controls is not feasible.
when available engineering controls are not sufficient to reduce exposure below appropriate
occupational exposure limits
during emergencies
in any situation where monitoring finds Acrylonitrile vapor concentrations above 2 ppm
Monitoring should always be performed in Acrylonitrile handling situations to establish the proper level
of personal protective equipment required.
Respiratory Protection Selection
All respirators used in Acrylonitrile operations must be designed specifically for use with Acrylonitrile. In
the United States, selection of a suitable respirator should be made from those approved by NIOSH.
Specific selection criteria include:
information on general conditions of use
physical, chemical and toxicological properties of Acrylonitrile
odor threshold data
NIOSH recommended exposure limit
OSHA permissible exposure limit
IDLH value
eye irritation potential
service life for canisters and cartridges
Respirators should be tested and service performed on a regular basis. Inspection and replacement of
worn or deteriorated parts must be performed regularly, as well as
regular cleaning and disinfecting. All respirator equipment should be stored in a clean, sanitary location.
