Professional Documents
Culture Documents
EO User Guidance
EO User Guidance
Introduction
1.1 Purpose
The purpose of this guide is to provide users of
Ethylene Oxide (EO) with a summary of the
essential information needed to safely handle
this important chemical product. The flam-
mable, reactive and toxic characteristics of
EO, and its effects on the environment, pose
risks that must be managed by all users and
producers.
This information is provided to the user as a
resource in the development of their safe
design, operation, maintenance, training and
emergency response practices. It is not our
intent to recommend any particular proce-
dure, equipment design or practice, but rather
to provide a summary of the authors current
state of knowledge relating to EO and its use.
Please note that this publication represents
the level of knowledge of its authors as of the
date of publication. The user should stay
abreast of new developments of information
about properties of EO, handling technology,
and regulatory requirements that occur after
publication.
1.2 Organization
In order to safely use EO, it is necessary to
understand its properties. The guide starts
with a discussion of physical and chemical
properties (section 2), followed by discussions
of health effects (section 3), and environmen-
tal effects (section 4). Section 5 discusses
safety incidents that have occurred in indus-
trial production, use, and transportation of EO.
Sections 6, 7, 8 and 9 discuss safe design and
operation of EO handling facilities. Sections
10 and 11 cover emergency response and fed-
eral regulations.
The appendices contain graphs and tables of
physical property data and a section-by-
section bibliography.
Editorial Committee
The following individuals were responsible for
their respective companies contributions to
the Guide:
Carey Buckles The Dow Chemical
Company
Pete Chipman Shell Chemical
Company
Mary Cubillas Shell Chemical
Company
Mike Lakin Celanese Ltd.
Dan Slezak The Dow Chemical
Company
David Townsend Celanese Ltd.
Keith Vogel Equistar Chemicals, LP
Mike Wagner Sunoco, Inc.
Acknowledgements
The editorial committee wishes to thank the
following individuals for their significant con-
tributions to this publication:
Ralph Gingell Shell Chemical
Company
Manuel Cano Equilon Enterprises LLC
ethyleneoxide
second edition
This guide represents a revision of the earlier publication of the same name issued in
September of 1995. It was produced through the cooperative efforts of Celanese Ltd.,
The Dow Chemical Company, Shell Chemical Company, Sunoco, Inc. and
Equistar Chemicals, LP.
Issue Date: August, 1999
Table of Contents
1. Introduction
2. Properties of Ethylene Oxide
3. Health Effects
4. Environmental
5. Overview of Hazards
6. Design of Facilities
7. Personnel Exposure
8. Equipment Preparation and Maintenance
9. Transportation & Unloading Operations
10. Emergency Response
11. Regulations
Appendix A: Tables and Figures
Appendix B: References
The information contained herein is accurate to the best of our knowledge. We do not suggest
or guarantee that any hazards listed herein are the only ones that exist. Use of this handling
guide is intended for persons with skill and at their own risk. User has sole responsibility to
determine the suitability of the product for any use and the manner of use contemplated. Any
potential health hazards associated with this product of which these companies may be aware
are described in the Material Safety Data Sheet (MSDS) for this product.
Online Viewing
The Guide is also available on the World Wide Web at http://www.ethyleneoxide.com.
2.1 Introduction
Properties of Ethylene Oxide
2-1
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Dedicated sources of inert gas (e.g., directly
from a high pressure pipeline or from high
pressure cylinders).
Area knockout pots on nitrogen supply lines
with high liquid level alarms or interlocks.
This design can prevent contamination of
EO with other chemicals or contamination
of other plant systems with EO.
Backflow prevention systems at each user. A
single check valve should not be relied on as
the sole means of preventing inert gas cont-
amination.
Continuous analyzers (for contaminants) on
inert systems.
Refrigeration
Refrigerated storage has the following benefits:
Lower temperatures decrease the rate of EO
polymerization, reducing potential for prod-
uct specification problems, and for problems
with tank nozzle plugging, etc. However,
lower temperatures reduce the solubility of
EO polymer and may cause the precipita-
tion of polymer that has already formed.
In case of contamination, refrigeration sys-
tems can remove all or part of the heat of
reaction. This can allow the reaction to be
controlled. At the minimum, it will allow
more time to implement control or disposal
measures.
Lower EO storage temperature allows a
lower inert gas pressure to maintain the
vapor space in the non-decomposable
region.
Lower temperatures will result in a smaller
fraction of EO being vaporized in the event
of a leak. The hazard of a pool of EO liquid
may be mitigated more successfully than
that of a vapor cloud.
Reference [7] contains a study of the relative
risks of storing EO at moderate temperature and
pressure versus low temperature and pressure.
EO storage refrigeration designs can either
incorporate refrigerated coils within the storage
tank or an external heat exchanger and circula-
tion pump. Internal coils can offer better heat
removal in the event of an exothermic reaction
within the storage tank. However, internal coils
can potentially contaminate the storage tank if a
leak occurs. Heat transfer fluids such as water or
glycols could react with the EO in the tank.
External heat exchangers may also contaminate
the tank contents, but the leak can be more
readily isolated.
In practice, storage temperatures range from
20F to 80F. Operating with temperatures in
the lower end of the range can result in precipi-
tation of EO polymer, especially if the EO had
been previously stored or transported at higher
temperatures.
Emergency Disposal of Tank Contents
An EO storage facility should be designed with
provisions to safely dispose of the inventory in
the event of a contamination reaction. Options
in current practice include:
Reacting the EO to glycols or other deriva-
tives by feeding to downstream users.
Depressuring the vessel. This can be to a
scrubber, a flare system, or to an elevated
discharge point. This can be a highly effec-
tive response, since evaporation of the EO
during this procedure provides an autorefrig-
eration effect which cools the vessel
contents.
Transferring to a holding system, such as a
pond, and diluting with water.
EO users must carefully consider the effects of
any of these actions (e.g., venting of EO) on
the health and safety of their workers and
communities, and on the environment. They
should only be taken as part of a well defined
emergency response plan.
6.6 Reaction Systems
Consider the following elements in design of
reaction systems:
Prevention of backflow from reactors into
EO storage.
Prevention of build up of unreacted EO.
Prevention of explosive mixtures in reactor
vapor space.
Design of Facilities
6- 8
Each of these elements is discussed below, as well
as reactor instrument and control design
philosophy.
Prevention of Backflow from Reactors
Catalysts in widespread use in EO reaction sys-
tems, such as KOH, have the capability to
initiate EO polymerization and accelerate other
reactions if they backflow into EO storage.
These reactions are exothermic, and can result
in uncontrolled heat release and vessel rupture.
Positive backflow prevention must be present
between storage and reaction systems (see sec-
tion 6.7 Prevention of Backflow/
Contamination).
Prevention of Buildup of Unreacted
Ethylene Oxide
Unreacted EO in a reaction system represents an
inventory of highly reactive material. The rate
of reaction is generally limited by the feed rate of
EO. The presence of higher than design quanti-
ties of EO can result in a reaction rate and
associated heat release that exceeds the capabili-
ties of the reactor control and safety systems.
An additional hazard occurs if reactor product
contains significant quantities of unreacted EO.
This can result in release of EO vapor from prod-
uct storage.
To avoid these conditions, the following must be
controlled within design limits:
EO addition rate
Mixing of reactants and catalysts
Concentration of catalyst
Reaction temperature
Prevention of Flammable Mixtures in
Reactor Vapor Space
The amount of diluent required to provide a
non-flammable mixture in the reactor vapor
space varies with temperature and unreacted EO
concentration. The reactor pressure control sys-
tem should be designed to provide adequate
diluent pressure to prevent flammable mixtures
over the range of reactor operation.
Reactor Design
Consider designing reactor cooling systems with
sufficient capacity to remove the heat generated
by an incipient runaway reaction.
Reactor vent capacity should similarly be sized
to control upset conditions.
Reactor Instrumentation & Control
Design Philosophy
Consider designing reactor control systems to
stop EO addition in the event of the following:
Excess rate of EO feed
Failure to add other reactants
Failure to add catalyst
Mixing system failure
High reactor pressure
Low reactor pressure
Reactor temperature control failure (high
ORlow reactor temperature)
Loss of utilities
Reactor instrument systems should also be
designed to give a good temperature profile for
detection of localized reactions.
Process analyzers can be used to continuously
determine EO concentration in reactor vapor
space and to stop EO addition when concentra-
tions approach the explosive range. When
process analyzers are used as part of a safety sys-
tem, adequate maintenance attention must be
provided to maintain high reliability. Analyzer
cycle time should be considered when relying on
a non-continuous analyzer to avoid unsafe con-
ditions.
6.7 Piping & Pumps
Piping
One effective element of a safe design is dedicat-
ing all appropriate piping systems exclusively to
EO service.
Carbon and stainless steels are suitable materials
6-9
for piping in EO service and should meet applic-
able ASME and ANSI codes. Stainless steel
offers the advantage of avoiding the potential of
rust formation associated with carbon steel lines.
EO polymerization can be a significant problem
in piping because of the relatively high amount
of surface area. Stagnant areas in piping systems
enable polymerization to proceed over extended
periods. Therefore, piping systems should be
constructed to avoid low points and dead spots.
Lines should be designed to be as short as possi-
ble with gravity drainage to points at which
contents can be purged from the system with
nitrogen. If emptying stagnant EO lines is not
feasible, for example in the case of a long EO
charging line to a batch reactor, a pipe loop that
circulates back to the storage tank may be con-
sidered. Chilled tracing of lines that may sit idle
can also reduce the polymerization potential.
All lines in EO service should be
clearly labeled.
Piping in EO service should use welded and
flanged construction. Screwed connections
should be avoided. The design process should
minimize the number of flanges. Each flange
represents a leak potential (including fugitive
emissions). Where flanges are necessary, they
should be fitted with gasket materials approved
for EO service.
Liquid EO should not be confined in lines
closed at both ends because heating
(atmospheric or otherwise) can result in high
liquid pressures, leading to bursting of the lines
or joints. If the confining of liquids is unavoid-
able, lines may be equipped with relief valves
with provision to capture vented EO and return
it to an appropriate location in the system.
Pumps
As part of the effort to reduce fugitive emissions,
practices in the industry are trending away from
the use of packed pumps and single mechanical
seals. Where packed pumps cannot be avoided,
packing material should be non-reactive in con-
tact with EO (e.g., flexible graphite). Pump
bodies should be of carbon steel, stainless steel
or ductile iron construction. Cast iron is not
acceptable.
Centrifugal pumps with double mechanical seals
are in widespread use for EO service. For double
seal pumps, an important criterion in the selec-
tion of a seal fluid should be its relative
non-reactivity in contact with EO. A 50%
aqueous solution of ethylene glycol (EG) as well
as pure diethylene glycol (DEG) have been used
successfully.
Magnetic drive pumps and canned motor pumps
have also been successfully used in EO service.
Proper specification of magnetic drive pumps is
dependent on accurate determination of NPSH
requirements, as these pumps are easily damaged
by cavitation. If a sealless pump with a magnetic
coupling is used, a strong magnetic filter on the
suction side of the pump is recommended to pre-
vent damage from metal particles entrained in
the product stream.
Pumps represent a potential source of ignition of
flammable vapors in an EO storage and process-
ing area, primarily due to the potential for
overheating. The preferred location for pumps is
in curbed areas separate from process or storage
areas. In general, good design practice will
include at least some of the following safeguards:
Minimum flow shutoff.
High (absolute) discharge temperature shut-
off.
High temperature delta (across the pump)
shutoff.
A system of detecting and alarming on
pump seal leakage.
Thrust bearing displacement shutoff (mag-
netic drive pumps).
A deluge system, activated manually, by
hydrocarbon leak detectors or by high tem-
perature.
Power usage monitors to shutdown pumps
on high or low power usage.
Automatic cooled bypass to pump suction
on high discharge pressure or low flow.
Valves
Selection of valves for EO service should con-
sider designs that do not trap EO in the valve
cavities where it can subsequently polymerize
Design of Facilities
6- 10
and render the valve inoperative. Valve selec-
tion should also consider the effectiveness of the
design in controlling fugitive emissions.
Experience indicates that gate valves, globe
valves and high-performance butterfly valves
perform well in EO service. By nature of their
design, ball valves and plug valves are subject to
polymerization problems.
Prevention of Backflow &
Contamination
It is essential to protect against backflow from
the process to storage. This is typically an instru-
mentation system providing tight shutoff on low
pressure differential between downstream users
and storage. Check valves should also be
included in the system, particularly at pump dis-
charges, but exclusive reliance on their
performance is not recommended. Should a
common EO source feed multiple process units,
isolation and backflow protection should be pro-
vided between EO storage and each unit and
between the separate units.
6.8 Handling of Vents & Effluent
Relief Systems
Pressure relief devices should be sized to relieve
pressure developed by the controlling contin-
gency identified for that process. A safety
analysis of the process must be conducted to
define the characteristics of the controlling con-
tingency. However, it should be recognized that
relief devices are unlikely to provide adequate
relief for such cases as explosive decomposition
of EO. Pressure relief valves for storage tanks
and for piping where liquid can be trapped
should be sized in accordance with practices rec-
ommended by NFPA 58: Storage and Handling
of Liquefied Petroleum Gases.
Industry practice is mixed with regard to the
routing of relief valve discharges. Some systems
are designed to vent to atmosphere; others tie
into a relief header system feeding a flare or
scrubber. If vented to atmosphere, discharges
from pressure relief devices should be designed
with adequate height and discharge velocity to
prevent contact of flammable vapor clouds with
ground level and potential ignition sources.
Automatic addition of steam to the relief valve
outlet piping can improve dispersion and reduce
flammability of the EO plume. Relief valve dis-
charge piping routed to the atmosphere should
be designed to minimize potential for human
exposure.
Design of relief systems in EO liquid or vapor ser-
vice should consider the potential for polymer
formation and plugging. EO polymer can form
in the piping upstream of relief valves, reducing
the valves capacity. Methods to protect against
plugging include:
Use of stainless steel piping.
Installation of rupture disks or rupture pins
underneath relief valves.
Minimization of piping distance (hence the
surface area available to support polymeriza-
tion) by fitting relief valves as close as
possible to the equipment they are
protecting.
Continuous injection of small amounts of
nitrogen directly under the relief valve and
directly after the relief valve if it discharges
into a header system.
Rupture discs or rupture pins may be useful in
minimizing fugitive emissions from relief valves.
However, their use as the sole means of pressure
relief is generally not recommended, as they can-
not reseat when the pressure excursion has
ended.
Vent Scrubbers
Aqueous systems for absorbing EO in process
vents are in widespread use in industry. These
systems can be designed for very high efficiency
of EO removal. However, the designer of a
scrubber system must take into consideration the
fact that EO/water mixtures are highly non-ideal
and use the Raoults Law deviation factors given
in Appendix A.
Vent gas is typically fed to a scrubber column
filled with random packing such as pall rings.
EO is absorbed by an aqueous stream running
countercurrent to the vent gas. Scrubbed gas
can be discharged to the atmosphere, subject to
environmental restrictions.
6- 11
Disposal of absorbed EO in scrubber effluent is
the major design problem. In general, the EO is
reacted to glycol. Either strong base or acid is
added to the absorbent stream as a reaction pro-
moter. However, acids are more effective
promoters than bases. Phosphoric acid, sulfuric
acid, and caustic soda are commonly used for
this purpose. Hydrochloric acid is not recom-
mended due to the potential to form
chlorohydrin. If this design practice is followed,
extreme care must be exercised to prevent acid
or alkali contamination of the process from the
scrubber system. (Figure 6.11)
Flares
Several EO producers and users successfully use
flares to handle EO containing vents. The most
important design consideration is preventing
decomposition flame propagation from the flare
tip back into the relief header system. The flare
designer must also be aware of the fact that con-
ventional flame arrestors have generally not
been tested on EO decomposition flames and
should not be assumed to be an adequate safe-
guard against decomposition flame propagation.
Thermal Oxidizers
Thermal oxidizers have been used to control EO
emissions from some processes. However, there
have been recent incidents in several thermal
oxidizers that control EO emissions, indicating
that some safety issues in these system designs
may not be fully understood at this time.
Sewer Systems & Waste Disposal
Facilities
If EO is drained (or could inadvertently be
drained) to a sewer system, the user should be
aware of the potential for EO emissions in the
sewer system and treatment facility, and the
potential for accumulation of flammable vapors
in the sewers, lift stations and waste water stor-
age tanks. Installation of online analyzers,
nitrogen purges and emission control devices
may warrant consideration.
It has been shown that wastewater containing
low concentrations (less than 1000 ppm) of EO
can be disposed of in biological waste treatment
facilities after proper acclimation of the system.
Section 4.2 contains a discussion of biotreat-
ment of Ethylene Oxide. The waste disposal
facility must be licensed to receive EO or other-
wise approved by a regulatory agency for this
service.
6.9 Miscellaneous
Electrical Equipment
Electrical area classification Class I, Division 1,
Group B or Class I, Division 2, Group B
(National Electrical Code [3]) should be used
where atmospheres contain or may contain EO
under normal or abnormal conditions. Group C
may be used if conduit seals comply with NEC
paragraph 501-5(a). Chapter 5 of the National
Electrical Code [3] deals with hazardous atmos-
pheres, classifications, and equipment
requirements. Additional references for area
classification can be found in API RP500 [4] and
NFPA 497A [2].
Other equipment, such as lighting fixtures, resis-
tors, solenoid coils, etc., must have normal
operating surface temperatures that do not
exceed the ignition temperature of EO. See
Section 501 of the National Electrical Code [3]
for further details.
Design of Facilities
6- 12
Reactor
Cooler
Makeup
Vent from
Process
EO Vent
Scrubber
To Atmosphere
Purge
Heater
Figure 6.11 Ethylene Oxide Vent Scrubber
System
6- 13
Fire Protection Systems
The user should consult NFPA 58, API 2510
and 2510A in designing fire protection systems
for EO storage and processing areas. Systems can
include passive (insulation) and active
(deluge/sprinkler) systems. Areas requiring del-
uge protection can be identified using process
hazards analysis methods which examine the
severity of the consequences of a fire scenario.
An ample fire water supply should be available.
The fire water supply should be sufficient to
ensure enough water to adequately dilute a spill.
Drainage should be designed with a capacity to
retain emergency water whether used for cool-
ing, fire fighting or dilution purposes. Storage
areas should be provided with diversion walls to
prevent the possibility of a pool fire underneath
vessels.
Leak Detection Systems
Combustible gas detectors are often used in
petrochemical processing plants. However, the
low concentrations of allowable exposure and
the low Reportable Quantity for environmental
releases make more sensitive leak detection
equipment desirable for EO processes. Gas
Chromatograph-based leak detection systems
sensitive to 1 ppm EO are in use both in process
plants and laboratories where EO may be pre-
sent. These systems generally have multiple
fixed sample locations connected to a single
analyzer.
Sampling Systems
Following are key design issues for sampling
systems:
The system should allow a representative
sample to be caught without releasing EO to
the environment or exposing the sample
collector.
Purging the sample connection with nitro-
gen and depressuring the sample system to a
vent collection system prior to disconnect-
ing the sample cylinder is recommended.
Dry-disconnect tubing fittings should be
considered for the connection from the sam-
ple tubing to the cylinder.
The system should prevent overfilling of the
sample cylinder with liquid. Overfilling
results in the potential for cylinder overpres-
sure from liquid expansion. Typical EO
sample cylinders are stainless steel, with an
internal dip tube to prevent overfilling with
liquid. The cylinder must be filled while
positioned vertically with the dip tube at the
top. The cylinders should be designed so
that only the valve with the dip tube can be
connected to the sample system.
Sample cylinders should be stored under
refrigeration while awaiting analysis and
again after analysis until disposal of any EO
remaining in the cylinder.
Unused EO remaining in the cylinder
should be returned to the process if possible,
or disposed of in an environmentally sound
manner.
Potential for personnel exposure to EO dur-
ing sample preparation and analysis should
be minimized by use of a laboratory hood.
Figure 6.12 EO sampling system.
Personnel Exposure
7.1 OSHA Ethylene Oxide
Standard
The EO standard was published in the Federal
Register on June 22, 1984 and amended on
April 6, 1988. The following is a summary of
its major provisions. The regulation, 29 CFR
1910.1047, should be consulted for specific
requirements.
Coverage
The standard applies to all occupational expo-
sures to EO. The only exception to this
coverage is the processing, use, or handling of
products containing EO where objective data
demonstrate that the product is not capable of
releasing EO in air above the action level or
excursion level under expected conditions of
processing, use or handling. Records of the
objective data must be maintained if the
exemption is used.
Exposure Limits
OSHAs Permissible Exposure Limits or PELs,
are the following:
1 ppm in air as an 8 hour time weighted
average (TWA) concentration
5 ppm 15 minute excursion limit (EL)
There is also an action level (AL) at 0.5 ppm
as an 8 hour TWA, which triggers certain
compliance activities such as exposure moni-
toring, medical surveillance and training.
Exposure Monitoring
Initial monitoring is required to determine air
concentration. If concentrations are above
the action level, periodic monitoring is also
required. Additional monitoring may be
required if process changes occur and employ-
ees must be notified of monitoring results.
Regulated Areas
Regulated areas must
be established wher-
ever occupational
exposure may exceed
the PEL or EL. Those
areas must be marked
and access limited.
Warning signs must
be posted around reg-
ulated areas stating:
Methods of Compliance
EO exposure must be limited through engi-
neering and work practice controls whenever
feasible. Where the PEL is exceeded, a writ-
ten program must be established and
implemented to reduce employee exposure.
OSHA recognizes that engineering controls
are generally not feasible for certain activities,
including loading and unloading of railcars,
vessel cleaning, and maintenance and repair
activities. In cases where engineering controls
are not feasible to prevent exposure above the
PEL, NIOSH approved respirators must be
worn.
Medical Surveillance Program
The employer must institute a medical sur-
veillance program for employees who are
potentially exposed to EO at or above the
action level (without regard to use of respira-
tors). Specific requirements for surveillance
and medical record retention are included in
the standard.
Training
Information and training must be provided to
any personnel who are potentially exposed to
EO at or above the PELs. Topics for training
are specified in the standard.
Product Exemptions
Products made from EO or containing EO are
exempt from the standard if objective data
shows they will not release EO at or above the
action level during normal handling or use.
DANGER
ETHYLENE OXIDE
CANCER HAZARD AND
REPRODUCTIVE HAZARD;
AUTHORIZED PERSONNEL
ONLY; RESPIRATORS AND
PROTECTIVE CLOTHING
MAY BE REQUIRED TO BE
WORN IN THIS AREA.
7- 1
7- 2
Written Emergency Plan
An emergency plan must be developed for
each workplace where there is a possibility of
an emergency. The employer must have a
means of promptly alerting affected employees
of an emergency occurrence.
Recordkeeping
The standard contains requirements for reten-
tion of medical and exposure records. Other
provisions of the standard also contain record-
keeping requirements.
7.2 Measuring Exposure
A number of methods are available for moni-
toring exposure to EO. Many of these involve
the use of charcoal tubes and sampling pumps,
followed by analysis of the samples by gas
chromatography. Sensidyne and Draeger mar-
ket hand pumps and indicator tube systems,
which do not require subsequent analysis,
with detection limits in the low ppm range.
Portable electrochemical EO detector/alarms
are available from Interscan and Draeger.
Dupont and 3M market passive badge-type
monitors for EO exposure.
OSHA has an extensive discussion of avail-
able methods for monitoring exposure to EO
(29 CFR 1910.1047), including an OSHA-
developed method.
7.3 Personal Protective Equipment
Eye Protection
All personnel in areas where EO is handled
must carry chemical goggles. Goggles should
be worn at all times in those areas in which
there is a risk of splashes from liquid EO. Face
shields (visors) provide additional protection
when performing any activity which has a liq-
uid exposure risk. Contact lenses should not
be worn where contact with EO can occur.
In the case of visor materials, the best EO
resistance is provided by fluorinated ethylene-
propylene (FEP) - polycarbonate composite.
FEP and PVC provide adequate resistance.
Protective Clothing
Many materials in common use are permeable
to or attacked by EO. Any materials proposed
for use in protective equipment that are not
known to be EO resistant, should first be
tested to establish their suitability. EO perme-
ation data for clothing and glove materials are
provided in Tables 7.1 and 7.2.
Permeation test data showed the following
equipment provides adequate protection in
EO service:
Suit: Kappler
1
Responder
and Responder Plus,
DuPont Barricade,
TYCHEM 9400 and
10,000. In cases where
there is concern of a flash
fire, consider using a
Kappler
1
Responder with
aluminized fiberglass or
PBI/Kevlar overcover.
Gloves: Safety 4-H
North B-131
Butyl Rubber
Silver Shield
Pioneer A-15
nitrile rubber
Boots: Butyl Rubber
Chlorinated Polyethylene
1. Registered U.S. Trademark of Kappler Europe Ltd.
Previously, Chemrel Max was a recommended
suit. However, it is no longer manufactured.
Other factors to consider in the selection of
protective clothing are durability, dexterity,
heat/cold resistance and whether disposable or
reusable clothing is preferred. If there is
potential for a flash fire, this factor should be
considered in the selection process. Either a
flash oversuit or an EO resistant suit incorpo-
rating flash protection should be considered.
PVC, nitrile rubber, neoprene, and Viton are
permeated rapidly on contact with EO. EO
and aqueous mixtures permeate leather.
Clothing subjected to EO contamination
7- 3
must either be discarded or decontaminated
before re-using. Clothing must be discarded if
it has been degraded or has absorbed EO.
Leatherwear contaminated with liquid EO
must be discarded because decontamination is
not practical.
Potential for EO exposure
When there is potential for exposure to EO
vapors or liquid, it is important to use the
proper protective clothing. EO can be
trapped against the skin and can cause severe
chemical blistering and burns, which take a
long time to heal. When released, EO liquid
will quickly change to vapor. If protective
clothing with open sleeves and legs is worn,
this vapor can readily get underneath the
clothing, resulting in burns. EO can also
penetrate protective clothing seams so it is
important to consider suit construction
as well.
Even dilute EO solutions can result in severe
chemical burns if the skin remains exposed to
the solution. Figure 7.1 is a chemical burn
resulting from 1.5 hours exposure to dilute EO-
water mixture absorbed into leather shoes.
Respiratory Protection
If the presence of EO in excess of exposure
limits is expected or detected, respiratory pro-
tection consisting of a NIOSH approved
respirator must be used. OSHA regulation 29
CFR 1910.1047 provides the following mini-
mum standards for respiratory protection for
airborne EO:
Airborne EO Minimum Required
(PPM) Respirator Type
Less than (A) Full facepiece with
or equal to EO approved canister,
50 ppm front or back mounted.
Less than or (A) Positive-pressure
equal to supplied air equipped
2,000 ppm with full facepiece, hood
or helmet,
or
(B) Continuous-flow sup-
plied air (positive pres-
sure) equipped with hood,
helmet or suit.
Above 2,000 (A) Positive-pressure self
ppm or contained breathing appa-
unknown (e.g., ratus (SCBA), equipped
emergencies) with full facepiece,
or
(B) Positive-pressure full
facepiece supplied air res-
pirator equipped with an
auxiliary positive-pressure
self-contained breathing
apparatus.
Firefighting Positive-pressure self-
contained breathing
apparatus (SCBA),
equipped with full face-
piece.
Escape Any respirator described
above.
Personnel Exposure
Figure 7.1 Chemical burn resulting from low
concentration of EO in water.
* NS - Not specified in test data.
NOTE: Breakthrough times are reported from data found in vendor and other databases. Some materials have
been tested more than once as indicated by multiple results. Formulation of clothing materials may
change, impacting break through times. Contact the supplier for specific product information or current
information on the testing of their products.
Table 7.1 EO Permeation Test Data for Clothing
7- 4
CLOTHING MATERIAL
ChemFab Challenger 5100
ChemFab Challenger 5200
DuPont Barricade
DuPont Barricade
DuPont Saranex R-23
DuPont TYCHEM 10,000
DuPont TYCHEM 10,000
DuPont TYCHEM 7500
DuPont TYCHEM 9400
DuPont TYCHEM 9400
DuPont TYCHEM SL
DuPont TYVEK QC
DuPont TYVEK-Polyethylene
coated
Fairprene Neoprene
ILC Dover Cloropel CPE
ILC Dover Polyurethane
Kappler CPE
Kappler CPF-3
Kappler CPF-4
Kappler Life-Guard Butyl
Kappler Responder
Kappler Responder
Kappler Responder Plus
Kappler Responder Plus
Mar-Mac Ultra-Pro Commander
MSA BETEX Butyl/Neoprene
Pioneer N-44 Neoprene
Wheeler Acid King Butyl
Wheeler Acid King PVC
Wheeler Acid King Teflon
VAPOR/LIQUID
NS*
NS
Liquid
Vapor
NS
Liquid
Vapor
Liquid
Liquid
Vapor
Vapor
Vapor
NS
NS
NS
NS
Vapor
Vapor
Vapor
NS
Liquid
Vapor
Liquid
Vapor
Vapor
NS
NS
NS
NS
NS
BREAKTHROUGH TIME, minutes
>950
31, 44, 64, 66
>480
>480
55, 6, 121, >400
>480
>480
53
>480
>480
immediate
immediate
<1
51, 158
118, 375
29, 65
80
>480
>480
44, 48, 52
>180
>480
>180
>480
>180
165
31
55, 85, 400
44, 13, 31
71
GLOVE MATERIAL
Ansell-Edmont 4H
Best 65NFW Natural Rubber
Best 6780 Neoprene
Best 878 Butyl
Best 890 Viton
Best Hustler 725R PVC
Best Nitri-Solve 727 Nitrile
Best Ultraflex 22R Nitrile
Best Ultraflex 32 Neoprene
Dayton Natural Rubber Surgical
North B-131 Butyl
North Silver Shield
Pioneer A-14 Nitrile
Pioneer A-15 Nitrile
Pioneer N-44 Neoprene
VAPOR/LIQUID
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
NS*
Vapor
Vapor
NS
NS
NS
Table 7.2 EO Permeation Test Data for Gloves
* NS - Not specified in test data.
NOTE: Breakthrough times are reported from data found in vendor and other databases. Some materials have
been tested more than once as indicated by multiple results. Formulation of glove materials may change,
impacting break through times. Contact the supplier for specific product information or current information
on the testing of their products.
BREAKTHROUGH TIME, minutes
>240
1
21
189
48
1
17
12
7
3, 5
>480
>480
32
195, >315
31
Personnel Exposure
7-5
Equipment Preparation
and Maintenance
8- 1
8.1 Preparation for Inspection or
Maintenance
General
When equipment in EO service must be
opened for testing, inspection, or repairs, all
precautions applicable to equipment handling
of flammable liquids and gases must be
observed. All EO must be removed from the
system and disposed of in accordance with fed-
eral, state and local regulations.
Contaminants such as oxygen, water, and
cleaning chemicals must be completely elimi-
nated before equipment is placed in or
returned to EO service.
Preparations for Entry
The user should follow the requirements of the
OSHA confined space standard (29 CFR
1910.146). Equipment should be cleaned and
purged of EO before beginning any mainte-
nance work. If it is impractical to reduce
airborne concentrations in and around the
equipment below 1 ppm, appropriate personal
protective equipment should be worn. All
maintenance work on EO equipment should
incorporate a safe work plan to ensure that all
personnel understand the hazards involved,
that proper personal protective equipment is
utilized, that applicable safety precautions are
observed in each work task and that other mea-
sures appropriate to working with EO are
observed.
Equipment being worked on must be thor-
oughly drained and blown free of liquid EO
with nitrogen. The equipment is then washed
with cool water and drained. Care should be
taken that hydrates are not formed during this
process, since the melting points of such mate-
rials can be as high as 52F (see Table 2.2, in
section 2). Rinse water should be disposed of
in a safe and environmentally responsible man-
ner. It should be noted that even dilute
solutions of EO in rinse water have caused
severe chemical burns (see section 7). Steam
purging or hot water washing may be further
required to remove EO polymer.
Prior to entry, the equipment must be isolated
from the process and from any potential hazard
source. Equipment atmosphere must be tested
for EO and proven safe to enter.
Persons entering equipment, vessels or any
confined space which has been in EO service
must be equipped with appropriate respiratory
protection (see section 7.3), unless it is demon-
strated that the atmosphere inside the
equipment, vessel or confined space is without
hazard and will remain so during the time peo-
ple are inside.
Special Problems with Ethylene Oxide
Polymer
In systems storing pure EO, it is common for
polymer to form and to accumulate gradually,
especially where the EO is relatively stagnant.
Polymer can retain EO after washing, which it
can gradually release even after the equipment
initially tests free of EO. After the initial purg-
ing and rinsing steps, good practice is to wait
several hours and retest prior to opening up to
the atmosphere.
Low molecular weight polymer can generally
be removed by steaming or washing with hot
water. Because hot water and steam would be
reactive with EO, the user must assure that free
EO has been removed before using hot water
or steam on equipment.
High molecular weight polymer must generally
be removed by physical means, such as high
pressure water blasting.
If polymer is present and time limitations or
other circumstances prevent warm water
cleanup, appropriate protection must be pro-
vided for personnel engaged in opening or
entering the vessel.
Polymer residues are both flammable and a
health hazard. They must be completely
removed and the equipment certified as being
free from all flammable residues and safe for the
intended work before undertaking hot work.
Mothballing
Equipment which has been in EO service, but
is being removed from service should be decon-
8- 2
taminated by washing or steam cleaning to less
than 1 ppm of EO. Such equipment should be
maintained under a nitrogen blanket and dis-
connected or blinded from live equipment.
8.2 Preparation of Internal
Surfaces
Foreign material on internal surfaces causes slow
self-polymerization of EO with an attendant
buildup of the polymerized material on those
surfaces. This self-polymerization can be mini-
mized by removing foreign matter such as
welding slag, loose debris and rust on internal
surfaces prior to putting them in service.
Cleaning can be accomplished by shot or grit
blasting, or by chemical methods. Shot blasting
creates dust and debris which must be removed.
Where equipment surfaces, such as pipework,
are inaccessible to blast cleaning, chemical
methods may be required.
Chemical cleaning involves the use of hazardous
materials and can cause damage to equipment if
not properly specified and performed. The use of
a qualified contractor is advisable. A variety of
chemical cleaning processes are available for
preparing metal surfaces for EO service depend-
ing on what surface contaminants are present,
including:
Alkaline or detergent degreasing, followed
by thorough rinsing.
Acid cleaning, if the metal is carbon steel. If
both carbon and stainless steel are present,
engineering advice should be obtained
before acid cleaning. Rinse thoroughly
afterwards.
Common acid cleaning uses EDTA or citric
acid. It may or may not be preceded by a
degreasing step. If the system contains mild
steel, a neutralization and passivation should be
performed. Sodium nitrite is typically used for
passivation. The system must be flushed clean
and dried by blowing with dry, hot nitrogen.
Equipment should be left under nitrogen pres-
sure until ready to receive EO. Failure to
adequately passivate or to keep material under
nitrogen blanket will result in significant rust
formation.
Caution:
It is extremely important to remove all
residues of cleaning chemicals, as EO may
react violently with them when the equip-
ment is put in EO service.
The effectiveness of a given chemical cleaning
procedure or the possibility of problems should
be evaluated using a test sample of the same
metal as the surfaces to be cleaned.
8.3 Leak Repair Clamps
Clamp-on or bolt-on, split body style leak repair
clamps have been used for temporary mitigation
of small ethylene oxide leaks from piping, valves
and vessels. These leak repair clamps can be
either purchased as off-the-shelf clamps or
engineered to fit, depending on the application.
The user must evaluate the risk of using clamps.
Many common sealants are not suitable for use in
EO service, and all sealants should be tested for
material compatibility and durability prior to use.
As with any moving stem valve, valves in ethyl-
ene oxide service may experience fugitive
emissions leaks. Ethylene oxide valve packing
glands should not be on-line repaired using the
drill-and-inject method due to the localized fric-
tional heat generated during the drilling on the
valve body.
8.4 Preventive Maintenance
Equipment containing ethylene oxide should be
on a routine preventive maintenance program
to insure proper operability. Internal inspections
should focus on monitoring equipment integrity
and detecting polymer formation. No flow or
low flow zones in a piping network and small
bore instrumentation tubing have the potential
for polymer buildup and should be included in
the inspection program. Nozzles for instrumen-
tation and inlets to pressure relief valves are
areas that should also be inspected on a routine
frequency.
Special considerations should be made for purg-
ing spare and offline piping and equipment to
prevent polymer formation.
Equipment Preparation
and Maintenance
9- 1
9.1 Regulations
EO is classified by the United States
Department of Transportation (DOT) as a
primary poison gas hazard with a subsidiary
hazard of being a flammable gas, and must be
placarded accordingly. Further, it carries the
materials poisonous by inhalation (PIH) des-
ignation by the DOT.
All persons offering a loaded or empty railcar
for transportation must meet the general
awareness and familiarization as well as func-
tion specific training requirements, as
specified in 49 CFR 172.704.
Special attention must be paid to the pressur-
ization of empty railcars for return to the
shipper. The objective is to maintain a non-
flammable vapor phase, as specified by DOT
Regulation CFR 49, Section 173.323(f), even
if the car heats up to 105F. Reference should
be made to the special railcar pressurization
criteria supplied by the shipper. For a given
unloading temperature, these criteria allow
for the extra nitrogen that is required for
safety over the entire range up to 105F.
See also section 11, Regulations Applicable
to Ethylene Oxide.
9.2 Railcars
Design
EO tank cars are designed to make the
transportation and handling of the material
safe and easy.
The DOT requires that EO be transported in
DOT class 105-J tank cars. All tank cars used
in EO service must have a tank test pressure
40' - 11" Truck Centers
51' - 10" Over Strikers
54' - 5
1
/
2
" Coupled Length
Center Line
of Angle Valve
13' - 11"
13' - 1
1
/
4
"
Top of Grating
2' - 10
1
/
2
"
4" Glass Wool Insulation Compressed to 3
1
/
2
" and
0.65" (Ceramic Fiber) Thermal Protection
Gauging Device, Safety Valve,
3
/
4
" Thermometer Well
3 - 2" Angle Valves &
1
/
4
" Sample Line Angle Value
116"
Inside Dia.
1
/
2
" Jacket Head
9
/
16
" Tank Head
9
/
16
" Tank
AEnd BEnd
Figure 9.1 DOT 105-J railcar for transporting Ethylene Oxide
Transportation &
Unloading Operations
10'- 5"
Over Grabs
B-End
15'- 4
15
/
16
"
of at least 300 psi by July 1, 2006 at the latest.
Most EO tank cars in service already meet this
requirement. DOT also requires EO tank cars
have a reclosing pressure relief device set to
function at 75 psig. These requirements are
specified in 49 CFR 173.323.
DOT class 105-J tank cars meeting the
required 300 psi tank test pressure are con-
structed from fusion welded carbon steel with
9
16" minimum plate thickness, and must have
an approved thermal protection system. A
typical thermal protection system consists of
0.65" of ceramic fiber surrounding the tank
shell, with 4" of glasswool fiberglass insulation
compressed to 3
1
2" by an outer metal jacket.
The outer metal jacket is 11 gauge (about
1
8")
carbon steel, except at the ends of the car
where tank puncture protection is provided by
1
2" head shields.
An EO tank car is designed for loading and
unloading from the top only with no bottom
fittings. The potential for leakage from dam-
aged tank fittings is greatly reduced in a
transportation incident when protected top
fittings and no bottom fittings are used.
EO in a tank car must always be kept under an
atmosphere of an inert oxygen free gas. Dry
nitrogen is typically used. No air should be
allowed to enter tank cars in EO service.
9- 2
Figure 9.2 Dome arrangement of a class DOT 105-J railcar for Ethylene Oxide service
Transportation &
Unloading Operations
Liquid Valve Magnetic Gauging
Device
Vapor Valve Thermowell
Safety Valve
Liquid Valve
Excess Flow Check Valves
EO tanks are equipped with float type excess
flow check valves below the liquid load/
unload valves and the vapor valves. This is a
safety precaution as the excess flow check
valves are designed to shut off the flow of liq-
uid or vapor if these valves are sheared off in a
derailment.
Caution:
Carbon dioxide is more than ten times as
soluble in EO as nitrogen and is not suitable
for blanketing or purging railcars or other
equipment containing EO.
An EO railcar (Type DOT 105-J) is equipped
with two eduction pipes/unloading connec-
tions, one vent for loading or vapor connection,
a gauging device, a reclosing pressure relief
device (safety valve), and a thermometer well
(thermowell).
If a liquid or vapor valve is opened too
rapidly, the excess flow check valve immedi-
ately closes, cutting off the flow of liquid or
vapor. If the liquid excess flow check valve
should happen to close while unloading at
less than 120 gpm, there may be a restriction
such as polymer in the line creating a higher
than design pressure differential. If the excess
flow check valve closes, the pressure needs to
be equalized to drop the float back down.
Equalizing the pressure can be done by closing
the load/unload valve on the liquid line.
Be aware that the vapor line excess flow
check valve can close if the car is depressuriz-
ing too rapidly. If the excess flow check valve
closes, a false reading of railcar pressure can
occur, as pressure is measured in the line
downstream of the car loading/unloading
valve.
The railcar could be mistakenly over-pres-
sured and lift the pressure relief device set at
75 psig. Again, by closing the load/unload
valve the pressure can equalize on both sides
of the excess flow check valve and gravity
should drop the float back into position. In
extremely unusual circumstances, the float
can get stuck closed if there is EO polymer
present in the vent line. Nitrogen pressure
may have to be supplied on the down stream
side to force the valve back down.
In all cases, problems such as malfunctioning
equipment, running gear or loading appli-
ances should be reported to the EO supplier.
Other than emergencies, repairs should only
be done with supplier approval, to ensure
material quality, equipment function and
design requirements are maintained.
Emergency repairs should be reported to the
supplier before putting the car in
transportation.
9.3 Preparation for Unloading
The user should develop and provide to
unloading personnel a detailed procedure
and checklist specifying each step of the
unloading operation and the precautions
to be observed.
An operator unloading log should be kept
to record key information (temperature,
pressure, etc.).
The receiver of EO railcars should moni-
tor temperature. The presence of higher
than normal temperature may indicate
the presence of contamination and the
potential for reaction in the railcar.
Section 5.2 discusses hazards of contami-
nation. Section 10 discusses emergency
response.
Railcar numbers and the seal numbers on
the dome of each car should be recorded
in the log.
The DOT car specification number on
the car must be 105-J100W or 105-
J300W. Ethylene Oxide and
Inhalation Hazard must be stenciled on
opposing sides of the railcar.
Check the dome to assure that the seal is
intact. If it is not intact, contact the rail-
road and the EO supplier.
9- 3
Before breaking the dome seal or initiat-
ing any testing or unloading action the
following precautions are suggested:
Keep in mind that EO is highly reactive.
The unloading area should be well-
ventilated and free of sources of ignition.
OSHA requires that exposures not
exceed either 1 ppm averaged for an 8
hour period or 5 ppm over a 15 minute
period (excursion level).
Use appropriate respiratory protection
(Section 7.3) when making/breaking
connections, and during EO product
sampling.
Know where safety showers and eye
wash facilities are located in the railcar
unloading area.
Know the location, in the unloading
area, of fire fighting equipment (extin-
guishers, fire monitors, hose reels, deluge
systems) and know how to use it.
Figure 9.3 Steps in preparation for unloading Ethylene Oxide
The DOT requires placement of blue signs that read Stop Tank Car Connected
or Stop Men at Work at appropriate spots.
Transportation &
Unloading Operations
9- 4
Lock out switches and install a
derail mechanism to prevent
collisions with other cars.
Set the hand brake.
Chock the car front and back of at least one wheel.
9-5
9- 6
Ground the railcar on its bolster or on the top working area.
Break the railcar seal.
Transportation &
Unloading Operations
9-7
Raise the dome cover. Inspect the area under the dome carefully.
Use caution as valves and devices under the dome could leak.
Measure and record the temperature of the EO in the railcar by
lowering a thermocouple or thermometer into the thermowell.
Allow several minutes for the temperature measurement to stabilize.
9- 8
Measure and record the outage level using the cars magnetic gauge rod.
Experience has shown that it is difficult to meet the 1 ppm exposure limit
when hooking up or disconnecting EO railcars. Operators should wear
respiratory protection equipment when making or breaking connections
on EO railcars.
Figure 9.4 Canister mask with
EO specific canister
Figure 9.5 Positive pressure, hose-
line type respirator
Transportation &
Unloading Operations
9-9
Remove plugs in both vapor and liquid lines.
9.4 Unloading
Figure 9.6 Steps for unloading Ethylene Oxide
Pipe extensions should be inserted into the valves so that connections
can be made outside the dome of the car. Be sure that pipe extensions do
not interfere with the proper operation at the valve operating mechanism.
Attach the unloading line to the liquid valve extension.
Off-loading can be accomplished by either pressuring or pumping EO
from the railcar. In either case, nitrogen is needed to replace the liquid
and to maintain tank pressure.
Check for leaks on hose connections prior to introducing EO.
Transportation &
Unloading Operations
9- 10
Nitrogen should be attached to the vaporline to allow maintenance of the
railcar nitrogen pad.
9- 11
Purge lines with nitrogen.
Install a pressure gauge on the vapor line. Measure and record pressure.
Monitor temperature and pressure throughout the unloading process.
Refer to Figure 6.4 in section 6 (Design of Facilities) for proper nitrogen
pressure to maintain a non-explosive EO vapor content. Minimum pres-
sures should be set at 35 PSIG and maximum pressures at 60 PSIG.
Carefully open the vent and liquid valves. Maintain railcar pressure in
non-explosive region during unloading by adding nitrogen.
Transportation &
Unloading Operations
9- 12
If sampling is part of your procedure, sample and obtain laboratory verifi-
cation before unloading the railcar. The sample cylinder should be
grounded to prevent static sparks.
Polymer has a tendency to build up in the railcar sampling line in cars
equipped with a sampling valve. Sampling from the offloading line
reduces potential for plugging.
The excess flow check device consists of a float that becomes buoyant at
high flow. Once closed, the excess flow check valve will not reopen
until the pressure differential on both sides of the valve is equalized.
Remember that the car pressure monitor is downstream of the vapor
check valve and therefore will not read car pressure if the check valve
is closed.
It is important to note that emptying a tank or a shipping container of liq-
uid EO does not remove the danger of vapor decomposition. In fact, an
empty vessel can be more dangerous than one filled with liquid. As long as
EO vapor remains in a vessel, full inert gas storage pressure must be
maintained.
When all EO is unloaded, blow the lines to storage until the tank indi-
cates nitrogen flow. Use nitrogen to raise the car pressure to the level
required for a non-combustible atmosphere as recommended by your
EO supplier.
Close the liquid and vapor valves.
Log the final temperature and pressure in the railcar.
Nitrogen in the unloading lines should be vented in a safe and environ-
mentally sound manner.
Disconnect all lines and remove valve extensions.
9- 13
Replace all plugs. Magnetic gauge and
thermowell caps should be hand tight-
ened. Others should be wrench-tight
to prevent leaks.
Close the dome cover and install and
secure the locking pin.
If placards are faded or torn, replace.
Disconnect ground wires.
Remove chocks, derails, and signs.
9.5 Shipping Data
9.6 Transportation Emergencies
In case of an emergency involving an EO
railcar, contact the emergency assistance
numbers provided in the shippers Material
Safety Data Sheet (MSDS).
Density Vapor Pressure
(lb/gal) (psia)
20
O
F 7.59 7.1
40
O
F 7.47 11.6
60
O
F 7.34 18.0
80
O
F 7.21 26.9
100
O
F 7.08 39.1
105
O
F 7.05 42.7
For additional assistance or
information call: CHEMTREC at
(800)424-9300 or (202)483-7616.
10.1 Overview
Every emergency situation will be different,
and it is not the intent of this publication to
provide recommendations for every situation.
This section will cover the unique hazards of
EO as they apply to emergency situations and
for specific emergency situations such as fire,
air release, etc. When preparing your emer-
gency procedures for handling EO, the MSDS
provided by your EO supplier should be
reviewed thoroughly.
Emergency responders must be properly trained
and equipped per OSHA standards on emer-
gency response and emergency fire protection
(29 CFR 1910.38, 1910.120 and Subpart L).
The first priority in responding to an emer-
gency situation is the safety of the emergency
responders, employees, and people in the sur-
rounding community. The second priority is to
determine the incidents impact on the sur-
rounding equipment, environment and
property, and to set a strategy to stabilize the
situation and minimize the impact. The third
priority is the conservation or protection of
property and the environment.
Downwind evacuation should be considered if
EO is leaking but not on fire. For large spills,
DOT recommends evacuating in all direc-
tions at least 400 ft. DOT further
recommends evacuation of downwind areas
to at least 0.2 miles (day) and 0.6 miles
(night). In case of small spills, evacuation of
downwind areas to at least 0.1 miles (day)
and 0.2 miles (night) is recommended.
If a tank or rail car is involved in a fire con-
sider initial evacuation for one mile in all
directions. If the fire is prolonged or uncon-
trollable, or if a container is exposed to direct
flame, evacuation for one mile in all direc-
tions for protection from flying debris if the
container should rupture violently. (1996
North American Emergency Response Guidebook)
10.2 Potential Hazards
Health Hazards
Liquid EO and EO/water solutions
Are extremely irritating to skin
and eyes
Can cause blistering and severe damage
Easily penetrate cloth, leather and some
types of rubber. Leather cannot be
decontaminated.
EO vapor can be absorbed by wet or sweaty
skin, with potential for serious chemical
burns.
Odor thresholds are much greater than
permissible exposure limits; overexposure
occurs before the odor can be detected.
Inhalation of EO vapors
Causes irritation of exposed surfaces
(eyes, nose, throat, and lungs)
Potential effects on central nervous sys-
tem include drowsiness, nausea,
convulsions and limb weakness
IARC (International Agency for Research
on Cancer) classifies EO as class 1 car-
cinogenic to humans (IARC 1994).
Water contaminated with EO evolves EO
vapor and can be a source of exposure.
See also section 3, Health Effects of Ethylene
Oxide, and section 7, Personnel Exposure.
Fire Hazards
Volatile flammable liquid with heavier
than air vapors that may travel consider-
able distance to a source of ignition.
Lower Flammable Limit: 2.6%. Upper
Flammable Limit: 100%
Fire impingement on EO-containing
equipment can result in container failure
and/or explosive decomposition.
Combustion products are irritating and
considered hazardous.
Emergency Response
10- 1
Water/EO mixtures can support combus-
tion if water/EO ratio is less than 22:1
(open areas).
In closed systems such as sewers, water/ EO
mixtures can potentially flash at dilution
ratios up to 100:1.
See also section 2, Properties of EO.
Hazards of Contamination
Reacts with water, evolving heat. In
closed containers, reaction may be self
accelerating, resulting in container rupture.
Contamination with acidic or basic materi-
als accelerates reactions with water.
Contamination of pure EO with acidic, or
basic materials; metal oxides, metal chlo-
rides, or active catalyst surfaces may cause
explosive polymerization.
May polymerize violently in container if
exposed to heat.
10.3 Fire Response
Extinguishing Materials
Carbon dioxide small fires only
Dry chemical small fires only
Alcohol foam
Water spray
Extinguishing Techniques
Stay upwind.
Avoid physical contact.
Wear self-contained breathing apparatus
(SCBA) and appropriate protective cloth-
ing. Wear full chemical protective suit if
contact with material is anticipated.
For a large fire in a storage area, use
unmanned hose holders or monitor nozzles.
Withdraw immediately in case of venting
safety device or discoloration of tank.
Keep fire-exposed containers and nearby
equipment cooled using water spray.
Minimum 500 gpm/point of flame
impingement.
The addition of warm (above 51F) water
to pools of liquid ethylene oxide may tem-
porarily increase vapor evolution.
If there is potential for container rupture,
runaway internal reaction, or heat impinge-
ment causing explosive decomposition,
consider evacuation for one mile according to
DOT recommendations.
Should a Fire be Extinguished?
Fire impingement on EO-containing equip-
ment can result in explosive decomposition.
Because of this, a responder should strongly
consider extinguishing a fire if there is poten-
tial for flame impingement on EO-containing
equipment, even if the source of hydrocarbon
feeding the fire has not been stopped.
10.4 Spill Response
General Information
Proceed with caution.
Restrict access to spill area.
Keep unprotected personnel upwind of
spill.
Avoid contact with spilled product.
Wear SCBA and a full chemical protective
suit.
Eliminate ignition sources.
Prevent liquid EO and contaminated
runoff water from entering sewers and con-
fined spaces.
Notify proper authorities as required by
regulations.
10- 2
If spill has the potential of entering a
waterway, notify downstream users of
potentially contaminated water.
Prevent intake of contaminated water into
boilers or industrial process equipment.
Use only equipment approved for flamma-
ble atmosphere in the vicinity of an EO
spill.
Be cognizant of the extremely volatile,
flammable, and heavier than air nature of
EO while planning the response.
Air Release
Techniques for responding to releases to the
atmosphere include:
Evacuate local and downwind areas as con-
ditions warrant to prevent exposure of
personnel and to allow vapor to dissipate.
Knock down vapor with water fog or spray.
Water fog or spray applied to EO vapors or
fumes will absorb a substantial amount of
EO.
Alcohol foam applied to the surface of liq-
uid pools may slow the release of EO
vapors into the atmosphere.
When using water spray, small quantities
are likely to make conditions worse
because of acceleration of vaporization.
Large quantities of water are necessary to
effectively knock down EO vapor and
dilute spills.
10.5 Contamination Response
Dispose of contaminated material as
quickly as possible by feeding to down-
stream users.
Reduce reaction rate by venting to a safe
location (venting results in auto-refrigera-
tion of the contained EO).
Drain contaminated material to a holding
pond or tank and dilute with water.
Slow temperature rise by removing heat
such as with a sprinkler system, cooling
coils or water deluge.
Evacuate area if rate of temperature increase
is rapid or uncontrolled.
10.6 Use of Water in Emergencies
In considering the use of water in emergency
response, the user should be aware of the
following:
Water can be useful for extinguishing EO
fires and cooling equipment subject to fire
impingement.
EO and water are completely soluble in
each other, and a water spray can be useful
in knocking down EO vapors. However, a
water spray directed on a pool of liquid EO
will increase evolution of EO vapors until
significant mixing and dilution of the liq-
uid EO have occurred.
Water/EO mixtures of less than 22:1 ratio
can support combustion in open areas. In
closed systems such as sewers, water/EO
dilution ratios up to 100:1 are required to
eliminate combustion potential.
From the above it can be concluded that the
maximum amount of water available should be
applied to an EO release.
EO also reacts with water. At ambient condi-
tions, the EO/water reaction occurs over days
and months. The responder should not hesi-
tate to apply water in situations where EO has
been released to the environment, since the
hazard of fire and personal exposure is far more
significant than the potential for an EO/ water
reaction.
In a closed container, however, the heat release
from the EO/water reaction can build up the
temperature, leading to an accelerating or
runaway reaction and loss of containment.
This potential exists unless the EO in the con-
tainer can be rapidly purged out or diluted to a
few percent weight.
Emergency Response
10- 3
11.1 Summary
The following federal regulations are directed
towards users and producers of EO and were
found by doing a scan of the Index to Chemical
Regulations. The scan was done by specifically
looking for federal regulations that mentioned
or referenced ethylene oxide. This list is not
represented as inclusive of all federal regula-
tions that apply to manufacturing and
handling EO. The list specifically does not
include:
Federal regulations promulgated after the
date of the scan.
State and local regulations.
The reader is also advised that there are
numerous regulations that may impact EO
operations that do not specifically mention
EO and may not have been picked up by
the scan.
11.2 Regulations Numerical
with Subject Listed
Commerce (Foreign Trade)
15 CFR 799 Commodity control list for
foreign trade (polymers).
Labor OSHA
29 CFR 1910 EO-specific regulations for
worker and workplace safety.
.19 Applies exposure section;
((h) OSHA 31:3110 and
31:4303) to exposure limit,
permissible; (.1047) to ship
repair, ship building, ship
breaking, longshore and marine
terminal activities and con-
struction work.
.119 Applies process safety
to facilities with EO in excess
of the threshold planning
quantity (5,000 lbs.). Elements
of PSM program include
employee participation; gener-
ation of process safety informa-
tion; process hazards analysis;
generation, review and update
of operating procedures; train-
ing; contractor relations;
pre-startup safety reviews;
mechanical integrity; permit
systems; management of
change; incident investigation;
emergency planning and
response and compliance audits.
.178 Prohibits use of powered
industrial trucks in hazardous
atmospheres; practically requires
a permit system covering use of
these vehicles in an EO plant;
((c) (2) OSHA 31:6505)
industrial trucks in atmospheres
containing hazardous concen-
trations.
.1000 Removes EO exposure
scenarios from this general sec-
tion on air contaminants and
references them to 1910.1047.
.1047
(A) Specific regulation covering
all exposure scenarios to EO
except those below the action
level (still requires retention
of objective data for exempted
operations).
(B) Establishes action level of
0.5 ppm, 8 hour time weighted
average.
(C) Establishes permissible
exposure limits of 1 ppm, 8 hour
time weighted average and 5
ppm excursion limit (15
minute average).
(D) Requirements for exposure
monitoring including initial,
periodic and termination sam-
ples; periodic sampling required
every 3 or 6 months depending
on exposure levels. Also includes
monitoring accuracy and
notification of employee
requirements.
(E) Requires establishment of
regulated areas where EO con-
centrations exceed 8 hour TWA
or excursion limit.
Regulations
11-1
(F) Delineates methods of
compliance with exposure
requirements including engi-
neering controls (preferred)
and personal protective equip-
ment. Also requires a written
compliance program, emergency
plan, leak detection surveys
with annual review and updates.
(G) Outlines approved respira-
tory protection, protective
clothing and equipment.
(H) Requires written emergency
response plan and employee
alerting procedures.
(I) Outlines mandated medical
surveillance plan; required for
all employees exposed at or
above the action level (0.5
ppm) for 30 days or more per
year, without regard to respira-
tory protection and any
employees exposed during an
emergency event. Exams must
be done prior to assignment to
the work area, annually, at
termination or reassignment,
after an emergency exposure,
where symptoms of overexpo-
sure exist or when the employee
requests medical advice con-
cerning the effects of current
or past exposure on reproduc-
tive capabilities.
(J) EO hazards communication
program requirements includ-
ing signs at demarcation zone,
labels on containers, MSDS on
site and employee training
programs (annual).
(K) Recordkeeping requirements
including objective data to sup-
port exempted operations,
exposure measurements
(30 year retention) and medical
surveillance records (duration of
employment plus 30 years
retention).
(L) Permits employee or designated
representative observation of
monitoring activities.
Appendices A, B, C and D cover non-manda-
tory samples of MSDS, substance technical
guidelines, medical surveillance guidelines and
sampling and analytical methods, respectively.
29 CFR 1926 Construction Standards
.55 Gases, vapors, fumes
dusts and mists. Refer to
1926.1147 for ethylene
oxide parameters.
.64 Process safety
management of highly
hazardous chemicals.
This regulation is similar to
1910.119 but applies to the
construction industry.
.1147 This is similar to
29 CFR 1910.1047. Again, it
applies to the construction
industry. Appendices A, B, C
and D.
Transportation
U.S. Coast Guard (Ports)
33 CFR 126 USCG Handling of explo-
sives or other dangerous car-
goes within or contiguous to
waterfront facilities.
.10 Designates EO as a
cargo of particular hazard.
Requires authorization of
waterfront facility to engage in
transfer operations. May be
waived by USCG.
Authorization includes mini-
mum requirements for guards,
smoking prohibitions, hot
work controls, vehicle con-
trols, electrical installations,
on-site emergency equipment,
storage requirements and
operating procedures.
33 CFR 127 USCG Hazardous materials
Transportation Final
Regulation
.1209 Respiratory protec-
tion. Each waterfront facility
handling LNG must provide
equipment for respiratory pro-
11-2
Regulations
11- 3
tection for each employee
of the facility in the marine
transfer area for LNG during
the transfer of one or more of
the following toxic LNGs;
anhydrous ammonia, chlorine,
dimethylamine, ethylene
oxide, methyl bromide, sulfur
dioxide, or vinyl chloride.
The equipment must protect
the wearer from LNGs vapor
for at least 5 minutes
33 CFR 154 USCG Facilities transferring
oil or hazardous materials in
bulk.
.0 Requirements for
facilities including operations
manual and procedures, equip-
ment specifications, vapor
control systems, standard spec-
ifications for tank vent flame
arrestors and detonation flame
arrestors.
33 CFR 160 USCG Ports and
Waterways Safety
.203(E) Requires notifi-
cation of USCG for arrivals,
departures, dock shifts and
hazardous conditions of vessels
carrying EO. May be waived
by USCG.
Environmental Protection Agency
42 USC 7412 Clean Air Act
Section 112 National
Emission Standards for
Hazardous Air Pollutants list of
pollutants section 112b
lists EO.
40 CFR 52 Illinois state implementation
plan (additional requirements).
.741 App. A Required con-
trol strategies for Cook, DuPage,
Kane, Lake, McHenry and
Will counties. Covers EO as
miscellaneous organic chemi-
cal manufacturing process.
Mandates additional control
strategies, record keeping, report-
ing, leak detection and repair.
Emission capture and control
techniques must be > 81%.
May be additional controls
where EO is part of other
processes covered elsewhere
in SIP.
40 CFR 60 Standards of performance for
new stationary sources cover-
ing VOC emissions from
SOCMI air oxidation processes,
equipment leaks, distillation
operations.
.489 Subpart VV (SOCMI
equipment leaks) Required
inspection program, correc-
tive action, QA/QC Programs
reporting and recordkeeping
for leaks associated with
pumps, compressors, relief
devices, sampling connections
and valves.
.617 Subpart III (SOCMI
Air Oxidation Unit Processes)
required control strategies,
emissions limitations, mon-
itoring, reporting and record
keeping.
.667 Subpart NNN (SOCMI
Distillation Operations)
required control strategies,
emissions limitations, moni-
toring, reporting and record-
keeping.
40 CFR 61 National emissions standards
for hazardous air pollutants
(NESHAP).
.340 Producers that manu-
facture EO by cracking hydro-
carbons are subject to this
bezene-in-wastewater
NESHAP because benzene is a
by-product of the process and
appears in certain wastewaters.
Control requirements are spec-
ified for drains, conveyances,
and treatment steps.
40 CFR 63 Maximum Achievable
Control Technology (MACT)
for certain listed Hazardous
Air Pollutants (HAP) includ-
ing EO and other HAP that
are present in EO manufactur-
ing facilities.
.100 Compliance with this
regulation began October 1994
for certain parts of the plants and
will be complete after April 1999
for all regulated plant elements.
40 CFR 68 List of regulated toxic
substances and threshold
quantities for accidental
release prevention.
.130 Table 1 lists EO with a
threshold quantity of 10,000
pounds based on the following:
a) Mandated by congress;
b) On EHS list, vapor pressure
10mm Hg or greater.
40 CFR 180 Pesticide residue tolerances on
agricultural commodities.
40 CFR 185 Pesticide residue tolerances in
food products.
40 CFR 261 Identification as hazardous
waste/inclusion on hazardous
constituents list.
.33(F) Classifies as a haz-
ardous/toxic waste any discarded
commercial chemical product
off-spec species, spill or con-
tainer residues. Does not apply
to process waste streams
(although SOCMI HON
would). EO is designated as
U115 (U list waste).
App. VIII Hazardous con-
stituents list (relates to 261.33
above).
40 CFR 266 Management of specific haz-
ardous wastes including where
burned for energy recovery and
burned in boilers and indus-
trial furnaces.
App. V Risk specific dosages.
App. VII Health based lim-
its/residue concentration limits
= 3 x 10
-4
mg/kg.
40 CFR 268 Land disposal restrictions
including technology based
treatment standards and maxi-
mum allowable constituent
concentrations in waste residue
.42 Establishes technology
based treatment standards for
U115 waste (EO) as follows:
(1) Wastewaters wet air
oxidation or chemical/elec-
trolytic oxidation followed by
carbon absorption or incinera-
tion (2) Non-wastewaters
chemical/electrolytic oxidation
or incineration.
.43 Establishes maximum
constituent concentrations in
treated waste residue which
will permit land disposal.
Wastewaters = .12 mg/l.
40 CFR 302 Designations, reportable
quantities and notification
requirements for CERCLA
hazardous substances.
.4 Designates EO as haz-
ardous substance under
CERCLA section 102(A)
with a final reportable quan-
tity of 10 lb.
40 CFR 355 Requirements for emergency
planning and notification
under CERCLA.
.0 Establishes threshold
planning quantity of 1000 lb.
for EO. Excess of this amount
triggers more stringent emer-
gency planning with local/
state response groups and
notification requirements.
App. A and B Superfund,
extremely hazardous and
threshold planning quantity.
40 CFR 372 Toxic chemical release reporting
.0 Community right to
know program components
applicable to EO plants.
Requires certain recordkeeping,
reporting thresholds and
schedules and notification to
11- 4
Regulations
buyer of EO of product infor-
mation and hazards.
.65 Superfund, emergency
planning.
40 CFR 414 Effluent guidelines and standards
for organic chemicals, plastics
and synthetic fibers.
.60(A) Regulates effluent
from EO plants under Subpart
F (commodity organic chemi-
cals). Requires use of BPC
(best practical control tech-
nology) and mandates maximum
effluent levels for BOD (bio-
logical oxygen demand), TSS
(total suspended solids) and
pH for existing and new
plants.
Transportation
U.S. Coast Guard (Shipping)
46 CFR 40 USCG Special carriage
requirements for EO transport
on vessels.
.05 EO specific requirements
for bulk shipment.
46 CFR 150 Subchapter 0 Certain bulk
dangerous cargoes
Compatibility of cargoes.
.0 Mandates certain
construction, ventilation,
equipment and operating
requirements. Tables I and II,
Compatibility of cargo on
tank vessels.
46 CFR 151 Subchapter 0 Certain bulk
dangerous cargoes. Barges
carrying bulk liquid hazardous
material cargoes.
.0 Includes requirements for
construction, ventilation,
equipment, operations, cargo
segregation, tank types, trans-
fer operations procedures,
emergency equipment, special
requirements, environmental
controls, electrical installation
and inspection periods.
.05 Bulk shipment minimum
requirements.
46 CFR 153 Subchapter 0 Certain bulk
dangerous cargoes Ships
carrying bulk liquid/liquefied
gas or compressed gas hazardous
materials.
.0 Includes requirements for
construction, ventilation,
equipment, operations, cargo
segregation, tank types, trans-
fer operations procedures,
emergency equipment, special
requirements, environmental
controls, electrical installation
and inspection periods.
46 CFR 154 Subchapter 0 Certain bulk
dangerous cargoes safety stan-
dards for self-propelled vessels
carrying bulk liquefied gases.
.0 Additional requirements
covering hull structure, stability,
tank arrangements, cargo con-
tainment systems, tank types,
cargo piping systems, hoses,
pressure and temperature con-
trols, electrical systems, fire-
fighting systems, ventilation,
instrumentation and operating
procedures.
11-5
Transportation Research and Special
Programs Administration
49 CFR 172 DOT/RSPA Hazardous
materials table
.0 Table providing chemical
specific requirements for haz-
ards class, identification num-
bers, packaging groups, labeling,
special requirements, quantity
limitations and stowage
requirements. Also covers
EO/CO
2
mixture and EO/
propylene oxide mixture.
Subpart with HAZMAT train-
ing requirements. References
CERCLA RQ = 10 lb.
.101 Subpart B Hazardous
Materials Table.
This table provides informa-
tion concerning the proper
shipping name, hazard class or
division, identification numbers,
packing group, label require-
ments, special provisions,
packaging authorizations,
quantity limitations and vessel
stowage requirements for
hazardous materials.
.101 (Appendix A) List of
hazardous substances reportable
quantities (RQ).
This Appendix lists materials
and their corresponding
reportable quantities (RQs)
which are listed or designated
as Hazardous Substances
under 101(14) of the compre-
hensive environmental response,
compensation and liability act
(CERCLA).
49 CFR 173 DOT/RSPA Shippers
General requirements for
shipments and packaging.
.304 Requirements for
charging of cylinders with
liquefied compressed gas.
.323 Chemical-specific
requirements for packaging
portable containers, tanks and
tank cars.
Note: 49 CFR is the same as BOE 6000-M
11.3 Shippers Requirements
Any person who offers EO (or any hazardous
material) for transportation must comply with
the following subparts of:
49 CFR 172 Subpart C (Shipping Papers)
Subpart D (Marking)
Subpart E (Labeling)
Subpart F (Placarding)
49 CFR 173 (Shippers) General require-
ments for shipments and
packaging.
Subpart G (Gases, preparation
and packaging).
.323 (Ethylene Oxide).
49 CFR 179 (Specifications for tank cars)
Subpart C (Specifications for
pressure tank car tanks, class
DOT-105).
.105-7(C) (Ethylene
Oxide).
11- 6
Regulations
Tables and Figures
Appendix A:
Figure 1 EO Liquid Density
Figure 2 EO Vapor Pressure
Figure 3 EO Liquid Heat Capacity
Figure 4 EO Liquid Viscosity
Figure 5 EO Liquid Thermal Conductivity
Figure 6 EO Heat of Vaporization
Figure 7 EO Vapor Heat Capacity
Figure 8 EO Vapor Viscosity
Figure 9 EO Vapor Thermal Conductivity
Figure 10 Freezing Points of EO/Water Mixtures
Figure 11 Saturated EO Vapor Cp/Cv Ratio
Figure 12 EO Vapor Density
Figure 13 EO Coefficient of Cubic Expansion
Figures 14, 15 Raoults Law deviation factors for EO/water mixtures
Table 1 Physical Property Equations
Table 2 Conversion Factors
Table 3 Henrys Law Constants (Atm/Mole Fraction)
Table 4 Henrys Law Constants (MPa/Mole Fraction)
A- 1
L b s / F t
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Appendix A:
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A-5
A- 6
Appendix A:
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3
0
.
4
E
t
h
y
l
e
n
e
O
x
i
d
e
V
a
p
o
r
H
e
a
t
C
a
p
a
c
i
t
y
0
1
2
0
2
0
0
2
4
0
1
6
0
4
0
8
0
S
A
T
U
R
A
T
E
D
E
O
V
A
P
O
R
I
D
E
A
L
G
A
S
Appendix A:
A- 8
F
I
G
U
R
E
7
:
C e n t i p o i s e
0
.
0
0
8
0
.
0
0
9
0
.
0
1
0
0
.
0
1
1
0
.
0
1
2
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.
0
1
3
F
I
G
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8
:
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x
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a
p
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r
V
i
s
c
o
s
i
t
y
T
e
m
p
e
r
a
t
u
r
e
,
F
0
1
2
0
2
0
0
2
4
0
1
6
0
4
0
8
0
A-9
F
I
G
U
R
E
8
:
B T U / F t * H r * F
T
e
m
p
e
r
a
t
u
r
e
,
F
0
.
0
0
4
0
.
0
0
5
0
.
0
0
6
0
.
0
0
7
0
.
0
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8
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9
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1
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0
1
1
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0
1
2
0
.
0
1
3
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0
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4
F
I
G
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9
:
E
t
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l
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n
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O
x
i
d
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a
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r
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h
e
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m
a
l
C
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n
d
u
c
t
i
v
i
t
y
0
2
4
0
1
2
0
2
0
0
1
6
0
4
0
8
0
Appendix A:
A- 10
F
I
G
U
R
E
9
:
A- 11
F r e e z i n g P o i n t , F
F
I
G
U
R
E
1
0
:
2
8
2
4
3
2
3
6
4
0
4
4
4
8
5
2
0
6
0
8
0
2
0
4
0
1
0
0
E
t
h
y
l
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n
e
O
x
i
d
e
i
n
W
a
t
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r
,
w
t
%
F
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e
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z
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g
P
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p
o
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n
t
1
7
0
F
F
I
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1
0
:
C
p
/ C
v
R a t i o
T
e
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,
F
1
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2
5
1
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3
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2
2
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6
1
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2
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1
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2
9
1
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p
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r
0
1
5
0
2
5
0
3
0
0
2
0
0
5
0
1
0
0
Appendix A:
A- 12
F
I
G
U
R
E
1
1
:
L b s / F t
3
T
e
m
p
e
r
a
t
u
r
e
,
F
0
.
0
0
.
5
1
.
0
1
.
5
2
.
0
2
.
5
F
I
G
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R
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1
2
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p
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r
D
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n
s
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t
y
0
1
2
0
2
0
0
2
4
0
1
6
0
4
0
8
0
F
I
G
U
R
E
1
2
:
A- 13
C o e f f i c i e n t o f C u b i c E x p a n s i o n p e r F
T
e
m
p
e
r
a
t
u
r
e
,
F
0
.
0
0
0
7
0
.
0
0
0
9
0
.
0
0
1
1
0
.
0
0
1
3
0
.
0
0
1
5
0
.
0
0
1
7
F
I
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1
3
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t
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C
u
b
i
c
E
x
p
a
n
s
i
o
n
0
1
2
0
2
0
0
2
4
0
1
6
0
4
0
8
0
Appendix A:
A- 14
F
I
G
U
R
E
1
3
:
A- 15
This page blank intentionally.
10
9
8
7
6
5
4
3
2
1
0 0.2 0.4 0.6 0.8 1.0
Mole Fraction Ethylene Oxide in Water
*** Any pressure units can be used, so long as the units for vapor pressure and total pressure are the same.
Water
Ethylene Oxide
Terminal Regions are Expanded in the Next Figure
psia
17
35
45
55
65
psia
65
35
D
i
D
i
=
y
i
P
t
x
i
(vp)
i
Where:
yi = mol fraction (EO or water) in
gas phase
xi = mol fraction (EO or water) in
liquid phase
Di = Raoult's Law Deviation Factors
from Figures 14 and 15
(no units)
(vp)i = pure component vapor
pressure at system temperature
Pt = total system pressure
***
FIGURE 14: Raoults Law Deviation Factors for Ethylene Oxide/Water Mixtures
Appendix A:
A- 16
8
7
6
5
4
0.02 0.04 0.06 0.08 0.10 0
psia
17
D
i
=
y
i
P
t
x
i
(vp)
i
14
12
10
8
0.94 0.96 0.98 1.00
Mole Fraction Ethylene Oxide in Water
D
E
O
D
H
2
O
35
45
55
65
psia
65
35
Mole Fraction Ethylene Oxide in Water
Where:
yi = mol fraction (EO or water) in
gas phase
xi = mol fraction (EO or water) in
liquid phase
Di = Raoult's Law Deviation Factors
from Figures 14 and 15
(no units)
(vp)i = pure component vapor
pressure at system temperature
Pt = total system pressure
***
FIGURE 15: Raoults Law Deviation Factors for Ethylene Oxide/Water Mixtures
*** Any pressure units can be used, so long as the units for vapor pressure and total pressure are the same.
A- 17
Table 1 Physical Property Equations
EQUATION COEFFICIENTS (ALL PROPERTIES IN SI UNITS)
PROPERTY UNITS A B C D
Solid Density KgMOL/M
3
2.75E+01
Liquid Density KgMOL/M
3
1.8360E+00 2.6024E-01 4.6915E+02 2.6960E-01
Coeff of Expansion per K 2.6024E-01 4.6915E+02 2.6960E-01
Vapor Density KgMOL/M
3
3.3904E+00 5.0556E-02 2.9010E-04 -7.6743E-07
Vapor Pressure Pa 9.1944E+01 5.2934E+03 1.1682E+01 1.4902E-02
Heat of Vaporization J/KgMOL 3.6652E+07 3.7878E-01
Solid Heat Capacity J/KgMOL
*
K 2.1143E+04 1.4903E+03 1.1881E+01 3.8745E-02
Liquid Heat Capacity J/KgMOL
*
K 1.4471E+05 7.5887E+02 2.8261E+00 3.0640E-03
Ideal Gas Heat
Capacity J/KgMOL
*
K 3.3460E+04 1.2116E+05 1.6084E+03 8.2410E+04
Second Virial
Coefficient M
3
/KgMOL 6.0016E-02 5.2057E+01 1.8056E+07 6.9368E+19
Liquid Viscosity Kg/M
*
S 8.5210E+00 6.3420E+02 3.3140E-01
Vapor Viscosity Kg/M
*
S 2.9540E-06 4.1720E-01 7.8740E+02 2.3580E+04
Liquid Thermal
Conductivity W/M
*
K 2.6957E-01 3.9840E-04
Vapor Thermal
Conductivity W/M
*
K 3.7880E-04 1.1150E+00 5.6410E+03
Surface Tension N/M 7.4730E-02 1.1410E+00
Appendix A:
Table 2 Conversion Factors
To Convert From To Multiply By Notes
KgMOL/M
3
Lb/Gal 0.3676 1
Pascals Lb
f
/sq in 1.45E04
J/KgMOL BTU/Lb 9.758E06 1
J/KgMOL
*
K BTU/Lb
*
O
F 5.422E06 1
Kg/M
*
S Centipoise 1E+03
W/M
*
O
K BTU/Ft
*
Hr
*
O
F 0.578
N/M Lb
f
/ft 6.852E02
Notes: 1. Only valid for Ethylene Oxide.
Note: The symbol
*
denotes multiplication. The symbol
^
denotes exponentiation.
T is temperature, deg Kelvin. Tr is reduced temperature, T/T critical.
A- 18
Henrys Law Constants can be used with the following
equation to determine solubility of these gases:
Where:
X
i
= mol fraction of gas (N2, Ar, Methane, or
Ethane) in liquid EO
Y
i
= mol fraction of gas in vapor space above
liquid EO
P
t
= total pressure, Atm
H
i
= Henrys Law Constant for gas, Atm
USABLE RANGE
MIN MAX
E K K EQUATIONS
161 Y = A + (B
*
T) + (C
*
T
^
2) + (D
*
T
^
3) + (E
*
T
^
4)
161 469 Y = A/(B
^
(1 + (1 - T/C)
^
D))
161 469 Y=(-D/C)*LN(B)*((1-T/C)
^
(D-1))
7.9840E-10 233 383 Y = A + (B
*
T) + (C
*
T
^
2) + (D
*
T
^
3) + (E
*
T
^
4)
1.0000E+00 161 469 Y = exp (A + (B/T) + (C
*
lnT) + (D
*
T
^
E))
161 469 Y = A
*
((1 - Tr)
^
(B + (C
*
Tr) + (D
*
Tr
^
2) + (E
*
Tr
^
3)))
25 161 Y = A + (B
*
T) + (C
*
T
^
2) + (D
*
T
^
3) + (E
*
T
^
4)
161 284 Y = A + (B
*
T) + (C
*
T
^
2) + (D
*
T
^
3) + (E
*
T
^
4)
7.3730E+02 50 1500 Y = A + B
*
((C/T)/SINH(C/T))
^
2 + D
*
((E/T)/COSH(E/T))
^
2
1.7212E+22 235 1500 Y = A + (B/T) + (C/T
^
3) + (D/T
^
8) + (E/T
^
9)
161 284 Y = exp (A + (B/T) + (C
*
lnT) + (D
*
T
^
E))
161 1000 Y = (A
*
T
^
B) / (1 + (C/T) + (D/T
^
2))
161 284 Y = A + (B
*
T) + (C
*
T
^
2) + (D
*
T
^
3) + (E
*
T
^
4)
273 1000 Y = (A
*
T
^
B) / (1 + (C/T) + (D/T
^
2))
161 469 Y = A
*
((1 - Tr)
^
(B + (C
*
Tr) + (D
*
Tr
^
2) + (E
*
Tr
^
3)))
Table 3 Henrys Law Constants (Atm/mole fraction)
T(F) Nitrogen Argon Methane Ethane
32 2800 1670 613 84.3
77 2180 1420 614 109
122 1820 1270 595 129
A- 19
Table 4 Henrys Law Constants (MPa/mole fraction)
T(C) Nitrogen Argon Methane Ethane
0 284 169 62.1 8.5
25 221 144 62.2 11.0
50 184 129 60.3 13.1
Xi=
Y
i
P
t
H
i
Section 2 - Physical Properties
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No. 6 (1974), pp. 1311-1318.
[2] A. Wurtz, Justus Liebigs Ann. Chem.,
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[3] Societe Francaise de Catalyse
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[10] Rebsdat, Siegfried, and Mayer, Dieter
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[11] A. Weissberger, Heterocyclic
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[15] B. Pesetsky, Chem. Eng. Prog. Loss.
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[18] D. R. Stull, AICHE Monograph Series,
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[19] T. H. Baize, Ind. Eng. Chem., 53
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[20] D. Conrad, Bundesgesundheitsblatt,
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[21] W. H. Perkin, J. Chem. Soc., 63 (1893),
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[22] Y. Hashigushi, Tokyo Kogyo Shikensho
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[23] J. Osugi, M. Okusima, and
M. Hamanoue, Koatsu Gasu, 8 (1971),
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[24] S. N. Bajpai, Chem. Eng. Prog. Loss
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[25] J. H. Burgoyne and K. E. Bett,
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[26] J. H. Burgoyne and K. E. Bett and
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[28] E. O. Haenni, N. A. Affens, H. G.
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Appendix B: References
B- 1
[29] L. Cider and L. Vamling, Ind. Eng.
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[30] D. N. Kirk, Chem. Ind., (London,
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[31] F. T. Bodurtha, Industrial Explosion
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[32] F. G. Eichel, Electrostatics, Chemical
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[33] Plant Operations Progress, Vol. 7,
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[34] D. D. Wagman, et al, The NBS Tables
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[35] CRC Handbook of Themophysical and
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[36] W. F. Giauque and J. Gordon, J. Am.
Chem. Soc., 71 (1949), pp. 2176-2181.
[37] NIST Website: http://webbook.nist.gov/
cgi/cbook.exe?Name=oxirane&Units
=SI&cTG=on&cTC=on&cTP
=on&cTR =on#Thermo-Gas
[38] Union Carbide Industrial Gases,
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[39] V. Schroder and D Conrad, Chem. Ing.
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[43] Shell Chemical Company Internal
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[44] Product Catalog from Polysciences,
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1997.
[45] Nye Clinton, Paul Matlock, 1,2-
Epoxide Polymers, Encyclopedia of
Polymer Science and Engineering, v. 6,
p. 234, John Wiley & Sons, New York
(1985).
Section 3 Health
[1] Occupational Safety and Health
Administration, 25 CFR Ch. XVII
1910.1047.
[2] IARC, Monographs on the Evaluation
of Carcinogenic Risks to Humans.
Some Industrial Chemicals, Vol. 60, pp.
73-160, 1994.
[3] T.H. Gardiner, J.M. Waechter, Jr., and
D.E. Stevenson, Pattys Industrial
Hygiene and Toxicology, Volume 2,
Part A. eds. G.D. Clayton and F.E.
Clayton. John Wiley, New York, 1993.
[4] EPA/FEMA/DOT, Technical Guidance
for Hazards Analysis, December 1987,
Appendix D.
[5] J.V. Setzer, W.S. Brightwell, J.M. Russo,
B.L. Johnson and D.W. Lynch,
Neurophysiological and
Neuropathological Primates Exposed to
Ethylene Oxide and Propylene Oxide.
Toxicol. Ind. Heath, 12, 667-82, 1996.
[6] W.M. Snellings, J.P. Zelenak and C.S.
Weil, Effects on Reproduction in
Fischer 344 Rats Exposed to Ethylene
Oxide by Inhalation for One
Generation. Toxicology and Applied
Pharmacology, 63, 382-388, 1982.
B- 2
[7] W.M. Generoso, K.T. Cain, C.V.
Cornett, N.L.A. Cachiero and L.A.
Hughs, Concentration-Response
Curves for Ethylene-Oxide-Induced
Heritable Tranlocations and Dominant
Lethal Mutations. Environmental and
Molecular Mutagenesis, 16, 126-131
1990.
[8] W.M. Generoso, C.T. Cain, L.A.
Hughes, G.A. Sega, P.W. Braden, D.G.
Gossless and M.D. Shelby, Ethylene
Oxide Dose and Dose-Rate Effects in
the Mouse Dominant Lethal Test.
Environmental Mutagenesis, 8, 1-7,
1986.
[9] W.M. Snellings, R.R. Maranpot, J.P.
Zelenak and C.P. Laffoon, Teratology
Study in Fischer 344 Rats Exposed to
Ethylene Oxide by Inhalation.
Toxicology and Applied Pharmacology,
64, 476-481, 1982.
[10] A.M. Saillenfait, F. Gallissott, P.
Bonnet, and J.C. Protois,
Developmental Toxicity of Inhaled
Ethylene Oxide in Rats Following
Short-Duration Exposure. Fundam.
Appl. Toxicol. 34, 223-227, 1996.
[11] A.S. Rowland, D.D. Baird, D.L.. Shore,
B. Darden and A.J. Wilcox, Ethylene
Oxide Exposure May Increase the Risk
of Spontaneous Abortion, Preterm
Birth, and Postterm Birth.
Epidemiology, 7, 363-368, 1996.
[12] G. Olsen, L. Lucas, and J. Teta,
Ethylene oxide exposure and risk of
spontaneous abortion, preterm birth,
and postterm birth (letter).
Epidemiology, 8, 465-6, 1997.
[13] V.L. Dellarco, W.M. Generoso, G.A.
Sega, J.R. Fowle, and D. Jacobson-
Kram, Review of the Mutagenicity of
Ethylene Oxide. Environ. Mol.
Mutagen, 16, 85-103, 1990.
Note: this is one of six papers in Volume 16 number 2
by EPA on ethylene oxide mutagenicity
[14] L. Rhomberg, V.L. Dellarco, C. Siegel-
Scott, K.L. Dearfield and D. Jacobson-
Kram, Quantitative Estimation of the
Genetic Risk Associated with the
Induction of Heritable Translocations at
Low-Dose Exposure: Ethylene Oxide as
an Example. Environ. Mutagenesis,
Vol. 16, No. 2, pp. 104-124, 1990.
[15] R.J. Preston, T.R. Fennel, A.P. Leber
and J.A. Swenberg, Recommendations
of the Genetic Risk Assessement for
Ethylene Oxide Exposures. Environ.
Mol. Mutagen, 26, 189-202, 1995.
[16] L. Golberg. Hazard Assessment of
Ethylene Oxide, CRC Press, Boca
Raton, FL, 1986.
[17] R.E. Shore, M.J. Gardner, and B.
Pannett, Ethylene Oxide: An
Assessment of the Epidemiological
Evidence on Carcinogenicity.
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Section 4 Environment
[1] Conway, R.A., et al., Environmental
Fate and Effects of Ethylene Oxide
Environ. Sci. Technol., Vol 17, No. 2,
pp. 107-112 (1983).
[2] Verschueren, K. 1983. Handbook of
Environmental Data on Organic
Chemicals. Van Nostrand Reinhold,
New York, NY.
[3] Hansch, C. and A.J. Leo. 1985.
Medchem Project Issue No. 26.
Claremont CA: Pomona College.
[4] Howard, P.H. 1983. Handbook of
Environmental Fate and Exposure Data,
Vol. IV. Lewis Publishers, Chelsea, MI.
[5] Lyman, W.J. et al. 1982. Chemical
Property Estimation Methods.
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[6] Pitter, P. and J. Chudoba. 1990.
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in the Aquatic Environment. CRC
Press, Boca Raton, FL.
[7] J.P. Dever, K.F. George, W.C. Hoffman,
H. Soo, Ethylene Oxide, Kirk
Othmer Encyclopedia of Chemical
Technology, 4th ed., Vol. 9, pp 915-959,
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[8] Means, J.L. and S.J. Anderson. 1981.
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for measuring biodegradability in aque-
ous environments., Water, Air, and Soil
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[9] Dow Chemical Company. 1975.
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[10] Hazardous Substances Data Bank
(HSDB), 1996.
[11] Bogyo, D. A., et. al. Investigation of
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80-005, Office of Toxic Substances, US
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[12] Atkinson, R., et. al., Lifetimes and
Fates of Toxic Chemicals in Californias
Atmosphere, ARB-R-88/345,
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[13] Atkinson, R., et. al., Lifetimes and
Fates of Toxic Air Contaminants in
Californias Atmosphere, ARB-R-
90/441, Statewide Air Pollution
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[14] Singh, H.B., et al., SRI International for
EPA-600/3-84-082, 1984.
[15] Meylan, W.M., et al., Atmospheric
Oxidation Program, pp. 26 and 35,
Lewis Publishers, 1992.
[16] Howard, P.H., Handbook of
Environmental Degradation Rates, pp.
144-145, Lewis Publishers, 1991.
[17] Berglund, R.L. 1988. Fate of EO in a
wastewater treatment facility. Paper
presented at the 1988 meeting of the
AICHE, March 6-10, New Orleans.
[18] Rajagopalan, S., R. vanCompernolle,
C.L. Meyer, M.L. Cano, and P.T. Sun.
1998. Comparison of methods for
determining biodegradation kinetics of
volatile organic compounds. Water
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[19] Canadian Environmental Protection
Service, Ethylene Oxide
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Information for Problem Spills,
May 1985.
[20] Bridie. A.L., C.J.M. Wolff, and M.
Winter. 1979. BOD and COD of some
petrochemmicals., Wat. Res. 13:
627-630.
[21] Bridie, A.L., C.J.M. Wolff, and M.
Winter. 1979. The acute toxicity of
some petrochemicals to goldfish., Wat.
Res. 13: 623-626.
[22] Heck, W.W., and E.G. Pires. 1962.,
Growth of Plants Fumigated with
Saturated and Unsaturated
Hydrocarbon Gases and Their
Derivatives, Ag. and Mech.
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[23] McGahey, C., C. and E.J. Bouwer.
1992. Biodegradation of ethylene gly-
col in simulated subsurface
environments., Water Science and
Technology, Vol. 26(1-2): pp. 41-49.
[24] 1993 Air Software Guide,
Environmental Protection. pp. 34-37,
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B- 4
[25] Hazardous Waste Treatment, Storage
and Disposal Facilities, U.S.
Environmental Protection Agency,
Office of Air and Radiation,
November, 1989.
[26] Wu, J.M., and Schroy, J.M., Emissions
from Spills, Proceedings of a Specialty
Conference on Control of Specific
(Toxic) Pollutants, Edward R Frederick
(Editor), Air Pollution Control
Association, Gainesville, FL, February
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[27] US EPA, Emission Standards Division,
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Section 5 - Overview of Hazards
[1] Kletz, T. A., Fires and Explosions of
Hydrocarbon Oxidation Plants,
Plant/Operations Progress, Vol 89,
No. 8, August 1993.
[2] Troyan, J. E. and LeVine, R. Y.,
Ethylene Oxide Explosion at Doe
Run, AIChE Loss Prevention
Symposium, Vol 2, pages 125-130, 1968.
[3] CEP Technical Manual on Loss
Prevention, Volume 2, AIChE, New
York, pages 125-130.
[4] Vanderwater, R. G., Ethylene Oxide
Tank Car Explosion, Chemical
Engineering Progress, pages 16-20,
Dec. 1989.
[5] J.H. Burgoyne, ICHEME Symposium
Series No. 25, 1969 p. 5.
[6] Viera, G. A., Simpson, L. L., and Ream,
B. C., Lessons Learned from the
Ethylene Oxide Explosion at Seadrift,
Texas, Chemical Engineering Progress,
Vol 89, No. 8, pages 66-75, August
1993.
Section 6 Design
[1] NFPA 58, Liquefied Petroleum Gases,
Storage and Handling (1986).
[2] NFPA 497A: Recommended Practices for
Classification of Class I Hazardous
(Classified) Locations for Electrical
Installations in Chemical Process Areas.
[3] National Electrical Code (NFPA 70).
[4] API Recommended Practice 500A:
Classification of Locations for Electrical
Installations in Petroleum Facilities.
[5] Britton, Laurence G., Spontaneous
Insulation Fires, AIChE Loss
Prevention Symposium, San Diego,
CA, August 18-22, 1990.
[6] Brockwell, J. L., Prediction of
Decomposition Limits for Ethylene
Oxide - Nitrogen Mixtures,
Plant/Operations Progress, Vol. 9, pages
98-102, April 1990.
[7] Marshall, J., Mundt, A., Hult, M.,
McKealvy, T., Meyers, P., and Sawyer,
J., The Relative Risk of Pressurized and
Refrigerated Storage for Six
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Appendix B: References
B-5