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DOW Epichlorohydrin
TM
Table of Contents
Introduction Pages 3-4
Product Stewardship 3
Responsible Care 3
Customer Notice 4
Responsible Care is a service mark of the American Chemistry Council in the United States
Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow
2
Introduction
E pichlorohydrin is a highly
reactive chemical intermediate
available since 1957 from The Dow
Chemical Company (Dow). Today, Product Stewardship
Dow is one of the largest producers
of epichlorohydrin in the world, with Dow and its employees have a
a capacity of more than 450,000 fundamental concern for all who
make, distribute, and use its
metric tons/year (more than 1 billion
pounds/year) from plants in Freeport, products, and for the environment in
Texas, U.S.A., and Stade, Germany. which we live. This concern is the
basis for our Product Stewardship
In its pure form, epichlorohydrin is a philosophy by which we assess the
clear, colorless liquid. The presence health and environmental
of both an epoxide ring and a information on our products and
chlorine atom in the molecule allows take appropriate steps to protect
epichlorohydrin to readily undergo a employee and public health and our
variety of chemical reactions with environment. Our Product
many types of compounds. This Stewardship program rests with each
versatility earns its wide use as a and every individual involved with
chemical intermediate. Dow products, from initial concept
Regardless of its uses, and research, to the manufacture,
epichlorohydrin must be handled sale, distribution, use, and recycling
carefully to protect the health of or disposal of each product.
employees, customers, the public,
and the environment. Although your Responsible Care
company is responsible for its own Dow has a long-standing policy to
safety procedures, our goal is to ensure that its operations do not
make that task easier with this have an adverse impact on the
manual. community or the environment. To
Read it prior to handling or using uphold this policy, Dow is committed
epichlorohydrin products, and use it to Responsible Care, a continuing
as a training tool for new employees. effort by the chemical industry to
For additional assistance, you can improve the responsible management
ask Dow to: of chemicals.
Support your engineering and Under Responsible Care, Dow
industrial hygiene monitoring complies with 10 Guiding Principles
programs; and Codes of Management Practices
DOWTM Epichlorohydrin
Make a pre-delivery evaluation of that cover all aspects of research,
your site and provide suggestions development, manufacture,
for improvement; distribution, transportation, use, and
Conduct on-site training for your disposal of products. These
employees; principles also extend to prompt
reporting, customer counseling,
Attend the first delivery to assist in
community awareness, support of
a safe and spill-free product
external research, participation with
transfer.
government and others, and
We want to put our experience with promotion of Responsible Care
epichlorohydrin to work for you. worldwide.
Responsible Care is a service mark of the American Chemistry Council in the United States
Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow
3
Dow recognizes that no single entity
can protect the quality of all of our
air and water. However, by working
together on a global basis, the public,
Introduction
4
Emergency Contact Information
DOWTM Epichlorohydrin
7
Figure 2: Vapor Pressure of Epichlorohydrin (1)
Properties and Uses
(1)
These are typical values only, and are not to be regarded as sales specifications; users are
advised to confirm for their operations.
(1)
These are typical values only, and are not to be regarded as sales specifications; users are
advised to confirm for their operations.
8
Table 3: Typical Reactions of Epichlorohydrin
R R1
C
O O O
Ketones CH2CHCH2CI + RCOR1 CICH2CHCH2
O
9
Properties and Uses
H H H CH3 H H H CH3 H H H
I I I I I I I I I I I
HCCCO C OCCCO C OCCCH
I I I I I I I
O H CH3 H O H CH3 H O
H n
10
Properties and Uses
Epichlorohydrin-Based Rubber
Epichlorohydrin is polymerized or
copolymerized with ethylene oxide to
form elastomers. These elastomers,
Ion Exchange Resins members of a family of specialty Agricultural Products
polyether rubbers, possess excellent
Epichlorohydrin is used to produce Biologically active compounds are
physical properties over a wide range
both anion- and cation-exchange prepared by reacting epichlorohydrin
of temperatures and are resistant to
resins. Water-insoluble anion- with alcohols or the sodium salts of
fuel, oil, and ozone. Other
exchange resins having good stability alkylphenols. Such products have
advantages are excellent aging
are prepared by reacting found effective use in insecticides,
characteristics, high resiliency, and
epichlorohydrin with bactericides, and fungicides.
flexibility at low temperatures.
ethylenediamine or a higher
homolog. Strong-base anion- Applications for epichlorohydrin- More Applications
exchange resins can be produced by based rubber include automotive and Other applications for derivatives of
reacting epichlorohydrin with aircraft parts, seals and gaskets, wire epichlorohydrin include:
polymeric tertiary amines. and cable jackets, adhesives,
Asphalt improvers
Epichlorohydrin-based anion packings, hose and belting, rubber-
coated fabrics, and energy absorbing Corrosion inhibitors
exchangers are used successfully to
purify drinking water and to clean units. Electrical insulation for wire
polluted air. Fire-retardant urethanes
Plasticizers Hair conditioning rinses
Cation-exchange resins are produced
The reaction of epichlorohydrin with Liners for polyethylene bottles
by condensing epichlorohydrin with
alcohols, alcoholates, or the sodium
polyhydroxy phenols and by Linoleum and linoleum cements
salts of stearic, oleic, palmitic,
sulfonating the product. Lubricant additives
myristic, and other fatty acids yields
products used as vinyl polymer Petroleum production aids
Surface Active Agents
plasticizers, solvents for food and Pharmaceuticals
Many epichlorohydrin-based,
flavoring, and plasticizers for Photographic film bases
surface-active agents are synthesized
polyurethanes. Rubber latex coagulation aids
by condensing the epichlorohydrin
with a polyamine such as Waterproofing compounds
tetraethylene-pentamine, plus a fatty Zinc electroplating compounds
acid such as stearic acid.
The polyamine and fatty acid may be
replaced with an alkali metal, starch,
or other reactant. Sulfonated
epichlorohydrin is occasionally
substituted for epichlorohydrin.
Such products find use in cosmetics
and shampoos, and as detergents,
sudsing agents, water softeners, and
demulsifiers.
11
Health, Safety, and Handling
Health Hazards
Odor Threshold and Warning Properties
Epichlorohydrin has a sweet, pungent smell with an odor threshold variously
reported at values less than 1 part per million (ppm) to 25 ppm. Sensory
perception studies have indicated that the mean threshold for odor recognition
of epichlorohydrin is 10 ppm, and that at 25 ppm it is recognized by the
majority of persons. These findings are supported by the epichlorohydrin
subcommittee of the Society of the Plastics Industry (SPI), in its publication,
Epichlorohydrin, Safety and Handling Guide, September 1994. Marked
nose and eye irritation occur only at levels that exceed 100 ppm.
Note: Workers must not rely on odor, or on eye and nose irritability, as a
warning or indicator of exposure potentials.
ppm by volume. The one-hour LC50 value is 3617 ppm for male rats and
2165 ppm for female rats.
Inhalation
Epichlorohydrin vapor is irritating to the mucous membranes of the
respiratory tract. Lung injury, which may be delayed, can result from
inhalation of epichlorohydrin vapor. Liver and kidney injury can result from
respiratory exposure or prolonged skin contact.
13
Health, Safety, and Handling
14
Health, Safety, and Handling
epichlorohydrin (see the NIOSH
Pocket Guide to Chemical Hazards,
Repeated skin contact even at a low or visit their website at www.cdc.
dose can lead to sensitization and gov/niosh/npg/npg.html.
Systems also must be designed to
allergic reactions. Further information on the health accommodate safety showers and
If respiratory distress develops, rest and environmental effects of
eye washes in the immediate area
and oxygen administration may be epichlorohydrin can be reviewed on (less than 8 meters [26 feet] apart)
helpful. Lung function should be the International Programme on where exposures are likely, such as
assessed following a significant single Chemical Safety (IPCS) INCHEM
truck or rail car off-loading stations
or intermittent inhalation exposure. document: www.inchem.org/ and locations where samples are
Persons receiving significant documents/ehc/ehc/ehc33.htm. taken. Showers and eye washes
exposures should be observed for 24- should be located so that workers
Exposure Control
48 hours for signs of respiratory whose vision is impaired by an
distress. Any significantly exposed Although epichlorohydrin has a very exposure can easily find them.
individual should be monitored for high vapor pressure, it can be
When respiratory protection is
liver and kidney function for at least controlled to maintain vapor
required for certain operations, use
60 days. Treatment is symptomatic concentrations well below
an approved full face air-purifying
and supportive if liver or kidney occupational exposure limits (see
respirator or a positive-pressure
injury occurs. Chemical burns of the Table 4). This should be achieved
supplied-air respirator, depending on
eye should be treated by a physician through properly designed, leak-tight
the potential airborne concentration.
experienced in dealing with chemical product handling systems. Good
If air-purifying respirator is used, it
eye injuries, but only after immediate ventilation is important; whenever
should be fitted with a fresh canister
and adequate decontamination with possible, the epichlorohydrin
for organic vapors or organic-vapor/
water. handling facilities should be located
acid-gas combinations.
outdoors to maximize natural
If lavage is performed, endotracheal
ventilation. However, good Note: Used canisters should be
and/or esophageal control is
ventilation cannot replace a closed, destroyed due to the poor odor-
suggested. Danger from lung
leak-tight system. Dow people have warning properties of epichloro-
aspiration must be weighed against
extensive experience in this area and hydrin which make odor an
toxicity when considering emptying
are prepared to help you evaluate unreliable indicator of chemical
the stomach. There is no specific
proposed equipment designs. We breakthrough.
antidote for epichlorohydrin.
can also provide information about
Provide supportive care. Treatment For emergencies and other conditions
the equipment used in our operations
should be based on the judgment of in which the exposure guideline may
(see Storage and Equipment, page
the physician and the patients be greatly exceeded, use an approved
31).
reactions. positive-pressure self-contained
All aspects of the handling operation, breathing apparatus (SCBA) or a
Exposure Limits from delivery through reaction to positive-pressure supplied-air
Government exposure limits are disposal, must be carefully respirator with an auxiliary SCBA.
subject to periodic revision. The scrutinized for exposure potentials.
Tanks and reactors must not be
information in Table 4 is given in Activities such as sampling should
entered until they have been washed,
good faith and believed to be correct receive particular attention.
purged, and tested for the presence of
as of April 2006. Note: The Measures that prevent exposures
epichlorohydrin vapor (see proposed
National Institute for Occupational should be thoroughly explored.
washing and tank entry procedures
Safety and Health (NIOSH) listing These include the use of vapor return
in section Storage and Equipment,
for the vapor concentration lines during product transfer, the dry
page 31). Safe oxygen concentrations
considered immediately dangerous to disconnect style of fittings for
(19.5-23.5 percent) should be
life and health (IDLH) is 75 ppm for transfer hoses, automated sampling
demonstrated with an oxygen
systems, and the like.
meter test.
15
Health, Safety, and Handling
16
Health, Safety, and Handling
Personal Protective
Equipment Is the exposure likely to occur only
All system designs should focus on once or twice per month as might
Air Monitoring eliminating the need for personal occur in some unloading
Due to its toxicity, high vapor protective equipment. However, operations?
pressure, and corrosive nature, personal protective equipment may be Is single-use equipment desirable?
epichlorohydrin can be safely required in certain operations, or in
Note: The MSDS/SDS on
handled in closed systems only. areas where exposure to vapor or
epichlorohydrin suggests that air
Because epichlorohydrin can be liquid is possible, such as in the event
purifying respirators, supplied air, or
absorbed through the skin in toxic of a system failure. The selection and
self-contained breathing apparatus
quantities, it is particularly important use requirements of personal
(SCBA) be used depending on
to avoid skin contact with vapor or protective equipment demand careful
conditions when respiratory
liquid. All operations must be management consideration. An
protection is required.
designed with engineering controls to overall appraisal should be made of
minimize personnel exposure (see the plant operation, exposure
Storage and Equipment, page 31). potentials, expected exposure Protective Clothing
Operations such as sampling, which duration, the specific activities being Even well-engineered systems will
are often considered open-system performed, and the training on require the use of personal protective
operations, should also be designed personal protective equipment being clothing in the event of spills or other
to avoid exposure. provided to workers. This appraisal potential exposure situations.
To ensure that epichlorohydrin is should be performed by a qualified In all operations involving
effectively contained, a formal air industrial hygienist in conjunction epichlorohydrin, and where employee
monitoring program should be with engineering, maintenance, exposure is possible, workers should
designed and implemented by a supervisory, and management staff. wear chemical workers goggles,
qualified industrial hygienist. This is An overall written plan to control safety hats, impervious boots, gloves,
particularly important for exposures should be developed. The and outer clothing (full body-
epichlorohydrin, which has poor plan should identify the types of covering impervious suits). Trousers
odor-warning properties (see Odor approved equipment (including should be worn outside the boots and
Threshold, page 12). The odor- manufacturer, make, and model); the sleeves should be taped to gloves
warning properties are not adequate types of protective equipment to use (with tapered sleeve inserts between
indicators of an over exposure for specific situations; the procedures sleeve and glove) to prevent contact
potential. for maintenance, cleaning, and of epichlorohydrin with the skin.
storage of the protective equipment;
The industrial hygienist should Clothing type, make, and materials of
required training; and other issues.
consider all aspects of the operation, construction should be carefully
Issues to consider when selecting
including work environment and job evaluated using an exposure control
personal protective equipment and
tasks. When changes are made in management approach that evaluates
managing equipment programs
procedures or equipment, sampling each exposure situation. For example,
include:
should be performed to verify protective clothing for splash
containment. A Dow industrial Is there a practical way to reduce protection (which is disposed of or
hygienist can assist with air the expected exposure by changes immediately cleaned after exposure)
monitoring and help determine in either equipment use or may not need to be as durable as
exposure levels in your operation. procedures? protective clothing for continuous
Talk with a Dow representative for Is the exposure likely to be at levels exposure situations. Carefully
more information. above the occupational exposure evaluate the data that is supplied by
limits (see Table 4)? your clothing manufacturer, paying
Is the exposure likely to be of very particular attention to the expected
short duration, after which clothing performance upon exposure
decontamination can be to epichlorohydrin. Important
immediately accomplished, or will a selection criteria are a high
lengthy exposure occur? breakthrough time and a low
permeation rate (see Table 5).
17
Health, Safety, and Handling
Sampling of Delivery
Vehicles
Sampling and analysis of the delivery
vehicle is the surest way to verify that
the product is epichlorohydrin.
Sampling systems must be designed
to avoid operator exposure. Many
such systems are commercially
available from specialty equipment
suppliers; some suppliers will design
a system specifically for your
purposes. The systems vary from
simple and low cost to very highly
automated and expensive systems.
Other systems of a less automated
nature are also available that control Perhaps the best place to take the sample is from the line through which the
exposures, but require more operator vehicle will be off-loaded.
training and care. Note: The use of the sampling port provided within the dome on rail cars in
An example of a simple, but safe and North America will usually produce a non-representative sample because the
effective sampling system which is line is often stagnant for long periods of time (the usual problems with
commercially available is shown in samples from the stagnant line are high color and non-volatile matter). If the
Figure 5. It is available from AZ- sample port is to be used, sufficient purge to completely clear it will be
Armaturen, www.az-armaturen.de. required.
19
Health, Safety, and Handling
20
Emergency Preparedness
A lthough the chemical industry has one of the highest safety records, it is
very important to put an effective, well-developed plan in place to ensure
quick and effective response to emergencies. Emergency preparedness should
consider all aspects of emergency situations that may occur on the site, in the
surrounding community, or in the community at large.
This section describes a process for emergency planning and provides specific
information about spills, fire-fighting, and associated waste disposal. Plans
should be developed with the assistance of local fire-fighters and community
groups. Several resources are available from the International Council of
Chemical Associations (ICCA), www.icca-chem.org; the American Chemistry
Council (ACC), www.americanchemistry.com; and the European Chemical
Industry Council (CEFIC), www.cefic.org.
Plan Development
The first step in emergency planning as defined by the ACC is crisis
management planning. This begins with a definition of potential crises that
require planning, and then moves through a number of steps related to
planning, preparation, mobilization, response, recovery, and post-incident
follow-up. The procedure should be comprehensive and consider all aspects
of potential emergencies, including warning alarms, evacuation assembly areas DOWTM Epichlorohydrin
and escape routes, personnel accountability, communication vehicles, chain of
command, notification of authorities, dealing with the media, and other
important concerns. If your plant does not have a crisis management plan,
one should be developed.
Responsible Care is a service mark of the American Chemistry Council in the United States
22
Emergency Preparedness
North America
CHEMTREC (CHEMical Table 7: Flammability Limits for Epichlorohydrin
TRansportation Emergency Center),
Flammability Limits LFL UFL
www.chemtrec.com, is committed to
Lower Limit Upper Limit
providing emergency response
personnel, law enforcement agencies, Epichlorohydrin in Air 3.8 % 21 %
and other interested persons with Oxygen in Epichlorohydrin Vapor 11.6%
information necessary to better
mitigate emergencies associated with The flash point of epichlorohydrin is 31C (88F), Tag Closed Cup (TCC).
hazardous materials. Exotherm begins at 325C (617F) and the auto-ignition temperature is 416C
(781F). The vapor is heavier than air and may travel considerable distance to
Europe a source of ignition and then flash back. The material is moderately soluble in
ICE (International Chemical water (6.6 percent at 20C/68F).
Environment, European Emergency
Response Network) www.cefic.org/ Fire-Fighting Methods
activities/logistics/ice/ice-guide.htm, is Use water fog, dry chemical, alcohol foam, or carbon dioxide when fighting
a cooperative program between fire. Use water to keep fire-exposed containers cool. If a leak or spill has not
chemical companies to prevent ignited, use water fog to disperse the vapors and to provide protection for
chemical transport incidents and to workers attempting to stop a leak. Water fog may be used to flush spills away
respond effectively if and when they from potential ignition sources.
do occur. Wear a positive-pressure, self-contained breathing apparatus if contact with
the vapors is possible; wear full protective clothing (see Health, Safety, and
Other Countries Handling on page 12).
Please refer to country-specific
For more information, review the local and country codes for fire protection
emergency organizations (see Table 6).
such as the National Fire Protection Association (NFPA), www.nfpa.org, the
European EN standards or the global International Electrical Council
Fire-Fighting Guidelines standards (IEC).
Fire Hazards Table 8: Fire Protection Standards
Epichlorohydrin is a flammable liquid Item North America Europe Pacific Worldwide
and its vapor forms explosive
Flammable and NFPA No. 30 EN standards Country-
mixtures with air.
Combustible Liquids specific
Although the lower limit for oxygen standards
concentration for epichlorohydrin
Electrical Codes NFPA No. 70 EN standards Country- IEC standards
flammability is 11.6 percent, Dow
specific
requires the concentration to be
standards
below 8 percent as a safety factor.
Protection Codes NFPA No. 780 EN standards Country- IEC standards
Hazardous Combustion Products specific
During a fire, smoke may contain the standards
original material in addition to
combustion products of varying
composition which may be toxic and/
or irritating. Combustion products
may include and are not limited to:
Hydrogen chloride. Carbon
monoxide. Carbon dioxide.
23
Emergency Preparedness
24
Emergency Preparedness
Waste Disposal Hydrolysis
Epichlorohydrin is classified as a The alkaline hydrolysis of dilute water solutions of epichlorohydrin to glycerine
hazardous waste in any part of the can, under certain circumstances, be a desirable way to handle very small
world. The relevant country-specific quantities of waste.
MSDS/SDS should be consulted for
specific government requirements Table 9: Epichlorohydrin Half Life, (T 1/2) in water @ pH 7
related to waste disposal. Customers Temperature (C) T 1/2 (h)
are advised to check their local 20 160
applicable government requirements.
30 5
Several methods of disposal are
available, including incineration, bio- In a solution of 4N NaOH, the highest reaction rate can be expected (half-life
treatment, and chemical conversion. approximately 15 minutes).
Applicable government requirements Note: The hydrolysis reactions of epichlorohydrin generate heat and a
must be considered prior to selecting a pressure build-up is a serious concern if the reaction is done in a contained
method. Final disposal methods system. Under alkaline conditions, the hydrolysis of epichlorohydrin proceeds
should be discussed with local to glycerine through an intermediate: glycidol. 2,3-Epoxy-propan-1-ol (note
authorities whenever possible. that glycidol is also toxic). The reaction rate is relatively slow at room
All applicable government temperature and can take days or weeks, depending upon circumstances, to
requirements regarding health, proceed completely to the final product, glycerine. The reaction rate increases
environment, and waste disposal must at elevated temperature. Treating large amounts (>100kg) of epichlorohydrin
be observed. Contact Dow for with dilute alkali at ambient temperatures with subsquent heating can lead to
additional information. an uncontrollable polymerization with excessive heat generation.
All quantities of epichlorohydrin - or If hydrolysis is considered, tests should be run to determine the exact chemical
waste material contaminated with make-up of the resulting mixture before proceeding with disposal. Large
epichlorohydrin - should be removed amounts of epichlorohydrin should be disposed of in an incinerator.
to an approved industrial waste
Note: Do not use sodium carbonate or other alkali as an absorbent for spilled
disposal area. If epichlorohydrin is to
epichlorohydrin.
be incinerated, only an approved
incinerator suitable for handling If removal of trace quantities of epichlorohydrin from equipment is the
chlorinated hydrocarbons can be objective, the use of low- or medium-pressure steam should be considered as
used. During incineration, hydrogen the first means to react it.
chloride is produced and must be
Hydrolysis at ambient temperatures at neutral or acid pH is not suggested
scrubbed out of the gas from the
because the reaction beyond the initially-formed chlorohydrins proceeds
incinerator.
slowly.
Water contaminated with
Contact your Dow representative if you wish additional information or
epichlorohydrin should be drained to
assistance.
a controlled area. This contaminated
water should be treated at an
approved water treatment facility.
When a problem arises as a result of a
major spill or equipment rupture,
only properly protected and trained
personnel should remain in the area
to supervise response and cleanup.
25
Delivery Procedures
T his section reviews road shipments and rail shipments, and provides a
delivery checklist for customer use.
Prior to delivery, customers should be prepared to safely receive and off-load
DOW Epichlorohydrin.
Note: Dow will not make deliveries to sites with which we are not familiar or
are not assured that personnel are capable of safe unloading and storage. In
general, this means that Dow will not deliver to a site that has not been visited
and reviewed by a Dow representative. Upon request, Dow technical
personnel will review the engineering plans of a proposed new facility and
provide feedback and suggestions.
Road Shipments
For road truck deliveries in North America, Dow uses a dedicated fleet of
trucks owned and managed by a single carrier. This carrier employs only
drivers who have received extensive training about the properties and hazards
of epichlorohydrin and the procedure in which delivery equipment must be
handled for a safe, spill-free delivery. These drivers can be a very useful
resource to assist your operating personnel with trouble-free transfers.
In Europe and other regions, the truck quantity deliveries are made in dedicated
intermodal containers (ISO-containers, 23 metric tons, volume 25,000 liters)
by a single carrier. A program of carrier appraisal and driver training is also in
place.
ISO-containers can be unloaded either from the top or from the bottom. The
standard valves sizes on the top are DN80 for liquid and DN50 for vapor.
The standard bottom valve type of an ISO-containers is a 3-inch BSP-
coupling.
To minimize personnel exposure to epichlorohydrin, Dow requires customers
to use their own dedicated hose permanently attached to their pumping
system. For this reason, Dow does not supply hoses or truck pumps.
Dow Product Stewards can provide product safety training for your
employees, and will also attend your first delivery. Talk to your Dow
representative or call your nearest Dow location for assistance.
Rail Shipments
Dow also ships product in a dedicated fleet of rail cars. These cars are 20,000
gallon (80 metric tons) pressure cars set up for top off-loading only. In North
America, these cars are all fitted with dry break fittings for both liquid and
vapor return. The fitting size is 2 inches for liquid and 1.5 inches for vapor.
The dedicated rail cars in Europe can load 65 metric tons (70 m3 volume) and
are designed for top and bottom discharge. The sizes of the connection flanges
in Europe are DN100 for liquid and DN50/DN80 for vapor.
Rail cars are not used in regions other than North America and Europe.
27
Delivery Procedures
Figure 8: Container Bottom Valve, 3-inch BSP Figure 10: Rail car Top Connections
28
Delivery Procedures
Are spotting, chocking, and brake
securement requirements clearly
Delivery Checklist identified?
The following checklist is designed to Note: For trucks, the driver should
help you prepare for a first delivery of have clear instructions to surrender Will a sample be drawn and
either a bulk truck, ISO-container or the keys and leave the truck cab. analyzed prior to off-loading?
a rail car to a new facility. For Note: Dow suggests sampling and
specific information about hardware, Is the operator required to use all of
testing to positively confirm the
see Storage and Equipment on the appropriate protective gear
product in the vehicle as epichloro-
page 31, or talk to your Dow Product (e.g., impervious suit, impervious
hydrin (see Sampling of Delivery
Steward. rubber footwear and gloves, hard
Vehicles, page 19).
hat, approved respirator) before off-
Has a Dow Product Steward visited
loading? What precautions will be taken to
your facility and reviewed your
bulk epichlorohydrin handling and Are the safety shower and eye wash avoid personnel exposure? Is
storage facility? Has Dow agreed to stations immediately accessible in personnel protective equipment
deliver to your facility? the off-loading area? Are they tested adequate?
before any connections are made to Are all lines and vessels properly
Note: Dow will not deliver to a
the vehicle? labeled and identified?
facility without performing an on-site
review to verify that it meets our Is the off-loading area cordoned off If connections have to be made on
required practices for bulk delivery. or barricaded to keep unauthorized the top of the transport vehicle, is
personnel and vehicles out? protection against falls adequate?
Have you arranged for a Dow Note: Are warning signs typically Was the oxygen level in the storage
Product Steward to attend the first used for the mode of transport used tank checked and verified to be
delivery? to secure the unloading area below 8 percent?
Was the off-loading piping and
Has the vehicles electrical ground Are all terminal lines plugged
valve system pressure-tested to
been verified? (blinded) to prevent spills from an
ensure that it is leak-free? If water
accidental valve opening (e.g.,
was used for the pressure test, how Has the off-loading operator
sampling and blow-down lines)?
was the system dried? Was the off- received training on the hazards of
the product and reviewed current Are a fire extinguisher and suitable
loading pump tested with liquid
MSDS/SDS? absorbent material available in the
after installation?
immediate area?
Note: Any water in the system will Has the driver received appropriate
training and instructions on the Is there a communication link to the
create quality and safety problems.
specific handling by the customer, if control room? How will it be
Is a written off-loading procedure the driver is supposed to assist maintained during off-loading?
available to employees? during offloading? Have calculations been made and
Was the procedure reviewed by the Dow can assist to help manage the confirmed to ensure that the load
off-loading operator? Will the training with the carrier personnel. will fit into the available tank
operator use it as a checklist for off- space?
Will a check be made of the
loading? vehicles number, seals, and product How will the transfer of the load
How will the vehicle be managed identification tag (on the off- into the tank be monitored to verify
for spill containment? Are there loading line) to verify the product movement of product when the
valve position changes required to against both the delivery note and pump is started and to ensure that
secure the containment system? If Certificate of Analysis? the product is going to the correct
so, are they described in the off- location? How will the movement
Note: Product stencils / label and
loading procedure? of vapors through the vapor return
accompanying documents on rail cars
Note: Dow suggests a spill- line to the vehicle be established
also should be checked.
containment volume great enough to and verified?
hold the entire contents of the vehicle
scheduled for off-loading.
29
Delivery Procedures
30
Storage and Equipment
T he guidelines in this section of the Epichlorohydrin Product Stewardship
Manual are general and should be used with information from tank and
equipment manufacturers and professional engineering firms. Dow Product
Stewards can help you evaluate engineering suggestions and can assist you
with ecological and product safety considerations.
Dow can provide technical assistance during equipment installation, review
your site prior to the first delivery, and assist your staff during that delivery to
ensure that minimum requirements are met for a safe, exposure-free delivery.
We can also review customer-supplied schematics of storage and off-loading
equipment, and make suggestions for improvement.
Contact your Dow representative for information, or call the Dow location
nearest you.
Materials of Construction
Carbon steel is satisfactory for the transport and storage of epichlorohydrin.
Steel is used for storage tanks, lines, valves, and fittings, and tank cars. Tank
trucks are usually of stainless steel construction. If the material will be stored
longer than 12 months, color may develop. In such cases, stainless steel tank
construction should be considered.
Cast iron is not recommended for auxiliary equipment, such as pumps and
valves, due to its brittleness.
Hazardous Materials
Warning: The following materials can create varying degrees of hazard due to
their incompatibility with epichlorohydrin.
Catalysts
Epichlorohydrin may polymerize spontaneously and with explosive violence
in the presence of catalysts such as acids, bases, and compounds having labile
hydrogens (Lewis acids). Back-flow into storage vessels or lines must be
prevented.
DOWTM Epichlorohydrin
32
Storage and Equipment
Figure 11: Typical Bulk Storage and Tank Truck Bottom Off-Loading System for Epichlorohydrin
Depad to
Vent Scubber
Deluge/Foam
4 To Process
1 1/2" Vapor
HLA Nitrogen
Epichlorohydrin 3 Valve or Vapor Line
3
LI 3 2 FI PI PCV 2 Safety shower
LT FT 1 PT
& Eyewash
TI FI
TT FT
FI PI To Deluge
FT PT 1 System
1 2" Liquid 4 Tank Truck
GAS EBV Fire
DET.
Monitor Vent to
Fire Safe Area
Ext.
Flex Hose
Foam
1 Stor.
Legend
PCV = Pressure Control Valve HLA = High Level Alarm TT = Temperature Transmitter PI = Pressure Indicator
ERV = Emergency Relief Valve LI = Level Indicator EBV = Emergency Block Valve PT = Pressure Transmitter
VRV = Vacuum Relief Valve LT = Level Transmitter FI = Flow Indicator GAS DET = Flammable Gas Detector
HLS = High Level Switch TI = Temperature Indicator FT = Flow Transmitter
This schematic drawing is provided in good faith by Dow. However, as the delivery, storage, use and disposal conditions are not within its
control, Dow does not guarantee results from the use of the schematic. The customer is advised to employ a qualified engineering service
to design and build their storage and handling facility. Since any assistance furnished by Dow with reference to the safe delivery, storage,
use and disposal of its products is provided without charge, Dow assumes no obligation or liability.
33
Storage and Equipment
Figure 12: Typical Rail Car Top Off-Loading System for Epichlorohydrin
To Storage Tank
2" Liquid 3
Nitrogen
2 Safety Shower
& Eyewash 4 To Sampling System
PI
Liquid
1 Discharge
Vent
1
Spl. Valve
Customer Access
Platform
Epichlorohydrin
Rail Car
Ground
(Optional Interlock with Off-loading Pump) Spill Containment Plan View of
(Remote) Rail Car Dome
Legend
PCV= Pressure Control Valve PI= Pressure Indicator
This schematic drawing is provided in good faith by Dow. However, as the delivery, storage, use and disposal conditions are not within its
control, Dow does not guarantee results from the use of the schematic. The customer is advised to employ a qualified engineering service
to design and build their storage and handling facility. Since any assistance furnished by Dow with reference to the safe delivery, storage,
use and disposal of its products is provided without charge, Dow assumes no obligation or liability.
34
Storage and Equipment
Figure 13: Unloading a Bulk Tank Truck
A Dow customer demonstrates a typical hook-up of a bulk tank truck with
dry disconnects
35
Storage and Equipment
36
Storage and Equipment
5. The remaining steps of the
Also, be sure that the tank and all cleaning procedure are dependent
metal piping and pumps are upon the type of lining and
electrically grounded. exterior paint on the tank, and
Tank Cleaning Procedures
See Figures 11 and 12 for further the amount of deposits in the
The following procedure to clean
instrumentation and control tank itself. These steps are
tanks containing epichlorohydrin is
suggestions. categorized as low-, medium-,
suggested.
Because epichlorohydrin may and high-temperature cleaning
Note: Tank cleaning will require procedures. Follow Steps 1-4
homopolymerize spontaneously and
personnel to enter the epichloro- above, then proceed with the
with explosive force (100 kJ/mol,
hydrin storage vessel. To ensure this steps described in the low-,
24.3 kcal/mol at 25C/77F) in the
is done safely, a detailed vessel entry medium-, or high-temperature
presence of catalysts such as acids,
procedure that includes the testing of categories.
bases, and compounds having labile
the environment in the tank should Note: It is very important to use the
hydrogens, it should be stored only
be developed by qualified personnel. following cleaning procedures
in tanks that have been thoroughly
The procedure should be used and regarding proper temperature limits
cleaned and dried, e.g., buffed and
signed by the responsible people, on linings, exterior paints, and
steamed, water-washed, and dried
including the operator and trades insulation, since most manufacturers
with an inert gas, such as nitrogen
person. guidelines do not have large safety
(See section Tank Cleaning
Procedures). factors. Linings and exterior paints
1. Use a pump to remove the
epichlorohydrin from the tank are very easily damaged by heat, and
Note: Combining epichlorohydrin
are expensive to repair.
and water can form a particularly until the pump loses prime.
hazardous two-phase mixture (see 2. Blind or remove all process piping Note: All water and epichlorohydrin
Properties and Uses, page 6, for from the tank to avoid accidental mixtures must be contained and
solubility information). Over time, flows into the tank during the disposed of as required by
an exothermic reaction will start at clean-up or tank entry regulations (see Waste Disposal,
the interface which can generate procedures. page 25).
enough heat to create pressure build- 3. Fill the tank at least half way with
up in the vessel. Such mixtures must water to remove any liquid Low-Temperature Cleaning
be disposed of promptly (see Emergency pockets of epichlorohydrin. If the
This type of procedure should be
Preparedness, page 21, for disposal tank is too large or disposal of
used for any tank that is lined,
information). water is a problem, this step may insulated, or painted with a material
be omitted if the following Step 4
Great care must be taken to prevent that is not capable of withstanding
is performed.
back flow or other inadvertent above-ambient temperatures.
addition of reactive materials to the 4. Water-wash for at least 8 hours
5a. Continue washing with the
storage tanks. Prior to start-up, a using some form of multi-
multidirectional spray nozzle set-
process hazards analysis should be directional spray washing nozzle
up for an additional 12-16 hours.
performed to identify flow, (e.g., the type used to wash tank
Open all drains on the tank.
temperature, pressure, equipment trucks or cars). Alternatively a
10 percent Sodium hydroxide 5b. Connect an air-moving device
failure, operating errors, or other
solution can be used for about capable of quickly turning over
conditions that could create an
1 hour. the air volume in the tank.
unexpected hazard (see Emergency
Note: This step is essential to tank 5c. Test the tank environment for
Preparedness, page 21).
cleaning; it greatly minimizes the flammability, toxicity, and
amount of epichlorohydrin that oxygen content. See under tank
could vent out in the following steps. entry below.
5d. If the air test results show that it
is not acceptable to enter,
continue to wash the tank until
acceptable limits are reached.
37
Storage and Equipment
Medium-Temperature Cleaning
This type of procedure is appropriate 5d. Turn off the steam, connect an air-moving device, and cool the tank down
for tanks that are lined, insulated, or to ambient temperature.
painted with a material capable of 5e. Test the tank environment for acceptable levels of flammability, toxicity,
withstanding boiling water up to and oxygen content as outlined in the tank entry section below.
100C (212F), but not direct
5f. If any tests show that it is unacceptable to enter, the tank should be further
steaming.
steamed until acceptable limits are reached.
5a. Open a vent valve at the top of
the tank and fill the tank 80 Tank/Vessel Entry
percent with water. A written tank entry procedure should be in place. This procedure should
5b. Connect a steam hose to the regulate which tests have to be done prior to the approval of tank entry by a
bottom of the tank and introduce responsible person. Required tests are oxygen content, flammability,
steam. Raise the water detectable epichlorohydrin and electrical safety. Suggested additional tests are
temperature to boiling, then boil temperature (especially after steaming). The procedure should further regulate
the water for 6 to 8 hours. Be who gives the final approval for tank entry. Persons entering tanks should
careful not to overboil, causing wear appropriate personal protective gear.
water to exit the vent valve.
Table 11: Guidelines for Acceptable Tank Entry
5c. Drain the water and purge the
tank to ambient temperature Conditions Acceptable Levels
with an air-moving device. Flammability Essentially zero
5d. Test the tank environment for Toxicity Less than 0.5 ppm epichlorohydrin in vapor space
safe levels of flammability,
Oxygen content 19.5-23.5 percent
toxicity, and oxygen. See under
tank entry below. Temperature Less than 40C (104F)
5e. Repeat the boiling procedure if Note: If the tank contained other compounds, the environment should be
the air tests are unacceptable. tested for safe levels of those compounds, too. Check with the relevant
Continue until acceptable limits manufacturer for acceptable levels of entry.
are reached.
Recommissioning
High-Temperature Cleaning
Before filling a tank with epichlorohydrin, follow these steps:
Use this procedure for any tank that
is lined, insulated, or painted with a 1. Pad and de-pad with nitrogen until the measured oxygen content is 8
material capable of withstanding percent or less.
temperatures up to 250C (482F). 2. The tank must be dry. This can be assured by making a dew point
5a. Open the vent and drain valves determination on a representative sample of a nitrogen purge flow from
on the tank. the tank. A dew point of less than -40C (-40F), as measured by a dew-
point apparatus, is used at Dow as the acceptable level of dryness.
5b. Connect a low pressure (240
kPa, 2.4 bar, ~35 psig or less) 3. Ensure that all safety and other systems are reinstalled and tested to verify
steam hose to the tank and flow correct operation.
steam into it, making sure that Note: Nitrogen Hazard! A number of fatalities have recently been caused by
the tank does not over-pressure. persons entering into areas and equipment with oxygen-deficient atmosphere.
5c. Increase the tank temperature to If a person enters an atmosphere of nitrogen, he or she can lose consciousness
95C (203F) for 2 to 4 hours, or without any warning symptoms in as little as 20 seconds. Death can follow in
until no detectable epichloro- 3-4 minutes. A person falls as if struck by a blow on the head. All personnel
hydrin is remaining. should know that one deep breath of 100 percent nitrogen will be fatal.
Breathing is stimulated and controlled (cerebellum) by carbon dioxide present in
the lungs. 100 percent nitrogen will displace carbon dioxide completely. In the
absence of a carbon dioxide signal to the brain, breathing stops. Personnel
should not work in or enter atmospheres with oxygen concentration below 19.5
percent or above 23.5 percent, unless equipped with a self-contained breathing
apparatus or breathing air mask. This is also true of rescue personnel who can
be overcome by the same oxygen-deficient atmosphere as the initial victim.
38
Storage and Equipment
Table 12: Equipment Specifications
Equipment Specifications Dow suggests stainless steel (316 SS) equipment be used to store and handle
Examples below may be specific to epichlorohydrin. Carbon steel is also a suitable construction material.
North America. Check with your Gaskets Spiral-wound, 304 stainless steel or Monel winding, PTFE or
country standards or involve a local flexible graphite filler, 0.175" thick, API-601 for ASME/ANSI B16.5
engineering company. flanges, carbon steel centering ring, no inner ring.
Lines, valves, pumps, and fittings can Flat ring: filled PTFE, 1/16" thick, Gylon 3510, Blueguard 3700 or
be of ordinary carbon steel or ductile Durlon 9000.
iron. Dry Break Valves e.g Civacon for the 1 1/2" and 2" female couplers and male
Note: Do not use cast iron due to its adapters respectively.
brittleness. Also avoid aluminum, Note: dry-break couplings are currenly used only in North
magnesium, copper, tin, zinc, lead, America.
and their alloys due to their potential
reaction with epichlorohydrin. O Rings PTFE, EPDM, EPR, Viton, Kalrez 4079.
V Rings PTFE
Spiral-wound gaskets with
polytetrafluoroethylene (PTFE) filler, Pumps Seal-less pump, preferably magnetic drive used in clean service.
flexible graphite filler, or filled PTFE Mechanical seal pumps (centrifugal), double seal using non-toxic
gasket (e.g. Gylon 3510 or Durlon purge.
9000) have been used satisfactorily. Pump body duplex stainless steel; CD4M (cast) or 2200 series
Centrifugal pumps equipped with (plate) steel, ductile iron or 316 stainless steel.
dual mechanical seals or magnetically-
driven (seal-less) generally provide Volute case gasket, glass-filled PTFE or PTFE envelope.
good protection for workers. Seal Hard Faces Carbon/tungsten
When mechanically sealed pumps are Hoses Polypropylene lined with inner wire construction 316 SS. (e.g.
used a combustible gas detector (ex- Wilcox type 4091 or equivalent).
detector) is recommended. The gas Polypropylene with PVC linings and galvanized outer wire (e.g.
detector should be located near each Chemoflex 0416-PG).
epichlorohydrin pump to detect any
pump seal leaks. Tank Linings Unlined steel acceptable for most applications.
The number of flanged connections Contact your Dow representative for linings information.
should be kept at a minimum to Electrical Minimum-U.S. Class I, Division II, Group C.
minimize fugitive emissions. Exterior Classification
Maximum-Class I, Division I, Group C.
painting is also suggested.
Electrical motors should have individual high temperature
Threaded connections should be kept protection.
to an absolute minimum and no
All equipment should be grounded.
steam tracing should be used on
piping. Note: The customer is advised to employ a qualified engineering service to
Table 10, page 28 provides guidelines design and build its storage and handling facility. Since any assistance
for tank piping and other equipment furnished by Dow with reference to the safe delivery, storage, use and disposal
used for epichlorohydrin storage and of its products, is provided without charge, Dow assumes no obligation or
transfer systems. For specific liability.
information about tank hardware,
consult with a professional
engineering firm and, if desired,
discuss engineering specifications
with Dow. Talk to your Dow
representative or contact your
nearest Dow location.
39
Analytical Methods
P lease consult your Dow representative for analytical methods for testing
the quality of epichlorohydrin, analyzing trace amounts of epichloro-
hydrin in water, and monitoring epichlorohydrin (and diglycidyl ether) in air.
The Dow assay method for epichlorohydrin is applicable to epichlorohydrin
having 99.0 percent or greater purity. Impurities are determined and the sum
of those concentrations is subtracted from 100 percent. The complete Dow
analytical method (method ID: DOWM 100408) is available on request.
Note: Prior to conducting any tests on epichlorohydrin, however, see
Health, Safety, and Handling on page 12.
Legend
- AICS = Australian Inventory of Chemical Substances
- DSL = Domestic Substances List
- EINECS = European Inventory Existing Commercial Chemical Substances
- ELINCS = European List of Notified Chemical Substances
- ENCS = Inventory of Existing and New Chemical Substances
- ISHL = Industrial Safety & Health Law Inventory
DOWTM Epichlorohydrin
- KECI = Korean Existing Chemicals Inventory
- PICCS = Philippine Inventory of Chemicals and Chemical Substances
- SEPA = State Environmental Protection Agency China Chemical Inventory
- TSCA = Toxic Substances Control Act Chemical Substances Inventory
Sea
Proper shipping name EPICHLOROHYDRIN
Sea - IMO/IMDG Class 6.1
UN Number 2023
Label 6.1+3
Packing Group II
EMS 6.101
Marine Pollutant (Y/N) Y
Air
Proper shipping name EPICHLOROHYDRIN
Air-ICAO/IATA Class 6.1
UN Number 2023
Label TOX+FL
Sub Class 3
Packing Group II
Pack Instruction (Passenger) 609
Pack Instruction (Cargo) 611
42
Appendix
North America
Plastics Products Information Customer Information Group
+1 800 441-4369 (toll free in U.S.A.) from 8 a.m. to 5 p.m. Eastern Time or
+1 (989) 832-1426 from 8 a.m. to 5 p.m. Eastern Time
DOWTM Epichlorohydrin
+800 3 694 6367# (toll free) from 9 a.m. to 5 p.m. Central European Time
+800 783 825 (toll free) Italy
0800 99 5078 (toll free) South Africa
+32 3 450 2240 from 9 a.m. to 5 p.m. Central European Time
+32 3 450 2815 (24 hours fax)
#
International toll free call from Austria , Belgium, Denmark, Finland (prefix
990), France, Germany, Hungary, Ireland, The Netherlands, Norway,
Portugal, Spain, Sweden, Switzerland, and the United Kingdom.
Emergency Response
Terneuzen, Netherlands
+31 115 69 4982
Emergency Medical Information +31 115 69 4982
Benelux: Belgium/Netherlands
Terneuzen, Netherlands +31 115 69 4982
Finland
Hamina, Finland +358 5 730 2400
France
Drusenheim, France +33 388 53 3676
Germany
Stade, Germany +49 4146 91 2333
Product Safety Information, Rheinmuenster, Germany +49 7227 91 2200
Greece
Lavrion, Greece +30 2920 62297
Iberia: Spain/Portugal
Tarragona, Spain +34 977 54 3620
India
Mumbai, India +91 22 6797 8600
Italy
Livorno/Priolo, Italy +39 335 697 9115
Scandinavia: Sweden/Norway/Denmark
Norrkoeping, Sweden +46 8 640 9011
Switzerland/Austria
Product Safety Information, Rheinmuenster, Germany +49 7227 91 2200
Turkey
Dilovasi, Turkey +90 262 754 5174
United Kingdom/Eire
Kings Lynn, United Kingdom +44 1553 76 1251
44
Appendix
Asia Pacific
Customer Information Group
+800 7776 7776# (toll free)
+60 3 7958 3392
#
except Indonesia and Vietnam
Emergency Response
Australia
1800 033 882 (toll free)
China
+86 532 8388 9090
Hong Kong
+852 2431 3300
Indonesia
+62 254 57 1369
Japan
Emergency Response +81 120 00 1017
Product Safety Information +81 3 5460 2100
Korea
+82 2 551 0601
Malaysia
1800 80 1255 (toll free)
Philippines
+63 43 485 0411
Singapore
1800 332 3543 (toll free), +65 6332 3543
Taiwan
+886 49 226 0560
Thailand
+66 3 868 3210
Vietnam
+84 903 99 6653
45
Appendix
Latin America
Customer Information Group
+55 (11) 5188 9222
Emergency Response
Argentina
+54 (3476) 43 8600 or +54 (291) 459 1400 or +54 (291) 459 1563
Brazil
Guaruja +55 (13) 3358 8226
Bahia +55 0800 282 5015
Chile
+56 (41) 50 8300
Colombia
+57 (5) 668 8000
Costa Rica
+57 (5) 668 8000 or +52 (241) 412 7143
Ecuador
+57 (5) 668 8000
Mexico
+52 (241) 412 7143 or +1 800 369 0000 (toll free)
Dow U.S.A. Emergency 1 (979) 238-2112 or 1 880 369-2436
Peru
+57 (5) 668 8000 or +51 (1) 264 0012
Puerto Rico
+57 (5) 668 8000 or +52 (241) 412 7143
Venezuela
+57 (5) 668 8000
46
Contact Information:
North America: +1 800 441-4369
+1 (989) 832-1426
+1 (989) 832-1465 (fax)
Mexico: +1 800 441-4369
Brazil: +55 (11) 5188 9222
+55 (11) 5188 9749 (fax)
Europe: +800 3 694 6367
+32 3 450 2240
+32 3 450 2815 (fax)
Asia Pacific: +800 7776 7776#
+800 7776 7779# (fax)
+60 3 7958 3392
+60 3 7958 5598 (fax)
#
Except Indonesia and Vietnam
http://www.dowepoxy.com
Notice: No freedom from any patent owned by Dow or others is to be inferred. Dow assumes no obligation or liability for the information in this document. The
information provided herein is presented in good faith and is based on the best of Dows knowledge, information, and belief. Since use conditions at non-Dow
facilities are beyond Dows control and government requirements may differ from one location to another and may change with time, it is solely the Buyers
responsibility to determine whether Dows products are appropriate for the Buyers use, and to assure the Buyers workplace, use, and disposal practices are in
compliance with applicable government requirements. Consequently, Dow assumes no obligation or liability for use of these materials and makes no warranty,
express or implied. The user of the information provided is solely responsible for compliance with any applicable government requirements. NO WARRANTIES
ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. Dow
does not endorse any third party products referenced in this document.
References to Dow or the Company mean The Dow Chemical Company and its consolidated subsidiaries unless otherwise expressly noted.
47