Users Guide

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
61.62
1.46
1
.0
9

1
.
4
3

1
1
6
.
9

Figure 2.1 The Ethylene Oxide Molecule

EO (oxirane) is the simplest cyclic ether. It is
a colorless gas or liquid and has a sweet,
etheric odor. The structure of an EO mole-
cule is shown in Figure 2.1. The C-C bond is
short and the bond angles strained [1]. Note
that the atomic distances are given in
angstroms.
EO is very reactive, because its highly strained
ring can be opened easily, and it is one of the
most versatile chemical intermediates. EO
was first prepared in 1859 by Wurtz [2] using
potassium hydroxide solution to eliminate
hydrochloric acid from ethylene chlorohydrin.
The chlorohydrin process developed from
Wurtzs discovery and industrial production
began in 1914. The importance and commer-
cial production of EO have steadily grown
since then.
The direct catalytic oxidation of ethylene, dis-
covered in 1931 by Lefort [3], has gradually
superseded the chlorohydrin process.
Currently, EO is produced by direct oxidation
of ethylene with air or oxygen. Annual
worldwide production capacity exceeds 11
million tons, making it an important indus-
trial chemical. Virtually all EO produced is
further reacted (section 2.4). Its most impor-
tant derivative is ethylene glycol, which is
used for the manufacture of polyester and in
automotive antifreeze. Other EO derivatives
include surfactants, solvents, amines, and
poly(ethylene) glycols.
In addition to being a versatile and commer-
cially important compound, EO has been
involved in a number of serious incidents. It
is necessary to understand the properties of
EO to manage the risks of its use.
Important physical properties of EO are summarized in Table 2.1.
2.2 Physical Properties
2-2
Ethylene Oxide
Chemical Abstracts Name: Oxirane
PSUID Code: 1441
IUPAC Name: Oxirane
Chemical Abstracts Number: 75- 21- 8
Structural Formula: CH
2
OCH
2
Synonyms: Ethylene Oxide 1,2-Epoxyethane
Dihydrooxirene Oxacyclopropane
Dimethylene Oxide Oxidoethane
Epoxyethane
Other Names: Ethene oxide; ETO; Oxane; Oxirene, Dihydro-; Oxyfume; Oxyfume 12; T- Gas; Aethylenoxid; Amprolene; Anprolene;
Anproline; ENT- 26263; E.O.; 1,2-Epoxyaethan; Ethox; Ethyleenoxide; Etylenu tlenek; FEMA No. 2433; Merpol; NCI - C50088;
a,b- Oxidoethane; Oxiraan; Oxiran; RCRA waste number U115; Sterilizing gas ethylene oxide 100%; UN 1040; C
2
H
4
O [37].
Property SI Units Engineering Units Note
Molecular Weight 44.053 44.053
Critical Temperature 469.15K 384.8F
Critical Pressure 7,191 kPa 1,043 psia
Critical Volume 0.00319 cu m/kg 0.051 cu ft/lb
Critical Compression Factor 0.2588 0.2588
Melting Point 161.46K - 169.1F
Triple Point Temperature 161.46K - 169.1F 1
Triple Point Pressure 0.0078 kPa 0.00113 psia
Normal Boiling Point 283.6K 50.8 F
at 101.325kPa(1atm)
Liquid Specific Gravity 20C/20C 0.875 0.875
Liquid Volume 0.00113 cu m/kg 0.018 cu ft/lb 2
Coefficient of Cubical Expansion (20C) 0.00158/K 0.00880/F
Heat of Formation - Ideal Gas - 1,194.8 kJ/kg -513.8 BTU/lb
Heat of Formation - Liquid - 1766 kJ/kg -759 BTU/lb 3
Gibbs Energy of Formation - Ideal Gas - 300.3 kJ/kg - 129.15 BTU/lb 4
Gibbs Energy of Formation - Liquid - 267 kJ/kg - 115 BTU/lb 3
Absolute Entropy - Ideal Gas 5.52 kJ/kg*K 1.319 BTU/lb*F
Absolute Entropy (liq) 3.494 kJ/kg*K 0.835 BTU/lb*F 3
Heat of Fusion at Melting Point 117.5 kJ/kg 50.52 BTU/lb
Entropy of Fusion 0.73 kJ/kg*K 0.175 BTU/lb*F [36]
Standard Net Heat of Combustion - 27,649 kJ/kg - 11,889 BTU/lb
Heat of Solution in Water - 142.7 kJ/kg - 61.35 BTU/lb
Acentric Factor 0.197 0.197
Radius of Gyration 1.937E- 10 m 6.355E- 10 ft
Dipole Moment 6.3E- 30 C*m 1.889 Debye
Liquid Dielectric Constant 14.5 14.5
at 0C (32F)
Vapor Dielectric Constant 1.01 1.01 [10]
at 15C (54.5F)
Electrical Conductivity (liq) 4E- 06 Siemens/m 4E- 08 mhos/cm
van der Waals Volume 5.485E- 04 cu m/kg 0.008785 cu ft/lb
van der Waals Area 7.492E+06 m sq/kg 3.658E+07 ft sq/lb
Refractive Index, n
D
1.3597 1.3597 5
Flash Point <255.16K <0F
Flammability Limits 2.6- 100 vol.% 2.6- 100 vol.%
Autoignition Temp 702K 804F
Decomposition Temp 833.2K 1040F 6
Table 2.1 Physical Properties of Ethylene Oxide
Graphs and tables of selected temperature dependent properties of EO are provided in Appendix A.
NOTES:
1. Estimated to be equal to the melting point temperature.
2. Determined at the normal boiling point.
3. Estimated from CRC 1994 Handbook of
Thermophysical and Thermochemical Data.
4. Calculated from the enthalpy of formation and the
absolute entropy.
5. Determined at 280 K.
6. Decomposition temperature has been reported as low as
723.2K(842F)
WARNING: FLAMMABILITY LIMITS ARE DETERMINED AT 298K AND 1 ATMOSPHERE. HIGHER TEMPERATURES AND/OR HIGHER PRESSURES WILL
LOWER THE LOWER LIMIT.
Properties of Ethylene Oxide
2-3
Table 2.2 Physical Properties of Aqueous Ethylene Oxide Solutions [9,10]
Ethylene Oxide Melting Point Bubble Point Specific Gravity at Flash Point
Content, wt% F C F C 50/50F F C
10/10C
0 32 0 212 100 1.0000
0.5 107 41.5
1 31.3 -0.4 88 31
2 37 3
3 29.7 -1.3
5 29.1 -1.6 136.4 58 0.9977 28 -2
10 42.1 5.6 108.5 42.5 0.9944
20 50.7 10.4 89.6 32 0.9816 -6 -21
30 52 11.1 80.6 27 0.9658 -18 -28
40 50.7 10.4 69.8 21 0.9500 - 31 - 35
60 46 7.8 60.8 16 0.9227 - 49 - 45
80 38.7 3.7 55.4 13 0.9005 -63 -53
100 -169 -111.7 50.7 10.4 0.8828 -71 -57
Ethylene Oxide Water Mixtures
Table 2.2 shows some of the properties of
aqueous EO solutions. Of particular note are
the relatively high melting points, which are
due to hydrate formation [4]. Hydrates consist
of organic molecules enclosed in a cage struc-
ture. The highest melting point observed is
52F (11.1C) and corresponds to a hydrate
composition of C
2
H
4
O 6.89 H
2
O [5].
Liquid EO and water are completely miscible
in each other in all proportions.
EO/water mixtures are highly non-ideal and
do not follow Raoults Law. Raoults Law
deviation factors for EO/water mixtures are
shown in figures 14 and 15 in Appendix A.
Solubility of Ethylene Oxide Gas
The solubility of ethylene oxide gas in various
compounds has been measured and reported
at atmospheric pressure and 22-23C by
Chaigneau [41]. These compounds include
water, alcohols, hydrocarbons, oils, chloro-
compounds, esters, and waxes.
Solubility of Gases in Ethylene Oxide
The solubilities of gases in liquid EO vary,
increasing in the order nitrogen, argon,
methane, ethane. Earlier data [6] have been
revised [7]. Increasing temperature tends to
increase the solubility. The Henrys Law
Constants for these gases in EO at different
temperatures are given in Appendix A.
2.3 Reactive and Combustive
Properties
Understanding the reactivity and combustion
properties of EO is important in managing the
risks of its use. As outlined in chapter 5, it has
been involved in serious incidents.
Table 2.3 Heat of reaction of various
Ethylene Oxide Reactions at 25C
kJ/kg BTU/lb
Combustion -27,649 -11,889
Decomposition - 3,051 -1,312
Isomerization -2,621 -1,127
Polymerization -2,093 -900
Hydrolysis -2,081 - 895 (a)
Hydrolysis -1,996 - 858 (b)
(a) Calculated from heat of formation values in CRC
Handbook of Thermophysical and
Thermochemical Data, CRC Press 1994.
(b) Reference [9]
2-4
Combustion
EO is a flammable, explosible chemical. Its
fire and explosion characteristics are system
dependent. Some of these characteristics for
EO/air mixtures are as follows:
The minimum value cited for the lower
flammable limit of EO air mixtures is
2.6% [20].
The upper flammable limit is typically
stated to be 100%, since pure EO can
decompose in the absence of air or
oxygen.
The flammable range of EO-air mixtures is
accordingly 2.6-100%.
The autoignition temperature of EO in air
at 14.7 psia is 804F (429C) [21].
Figures 2.2 and 2.3 illustrate the flammable
limits for the EO, air and either nitrogen or
carbon dioxide ternary mixtures at atmos-
pheric pressure, i.e., 14.7 psia (101.325kPa)
[39]. The literature also indicates some vari-
ability in the boundary concentration
demarcation separating the flammable and
non-flammable regions; e.g. [38, 39]. Also, it
is important to recognize that mixture pres-
sure affects the flammability characteristics
too. Figure 2.4 illustrates the effects of
pressure on the flammability region for
EO/Nitrogen/Air. Thus, more or less inert
dilution may be required depending on
whether the pressure is greater or less than
atmospheric.
The flammable limits of other mixtures of EO
with inert gases and air can be found in the
literature, e.g., EO with H
2
O [22]; N
2
[23],
[22]; N
2
-H
2
O [24]; CO
2
-H
2
O [24]; CH
4
[15];
CO
2
[6], [22], [25]; C
3
H
6
[26]; C
4
H
9
[26];
Properties of Ethylene Oxide
FIGURE 2.2: Flammable Region of Ethylene Oxide/
Nitrogen/Air Mixtures
Initial Conditions:
Temperature: 20C
Pressure: 1 atm.
20 40 60 80 100 0
0
20
40
60
80
100
0
20
40
60
80
100
N
i
t
r
o
g
e
n

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
E
O

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
Air Concentration (% Vol)
Flammable Region
Flammable Region
20 40 60 80 100 0
0
20
40
60
80
100
0
20
40
60
80
100
Initial Conditions:
Temperature: 20C
Pressure: 1 atm.
FIGURE 2.3: Flammable Region of Ethylene Oxide/
Carbon Dioxide/Air Mixtures
C
a
r
b
o
n

D
i
o
x
i
d
e

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
E
O

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
Air Concentration (% Vol)
2-5
N
2
-air [6]; CH
4
-air [6]; CO
2
-air [20]; CF
2
Cl
2
-
air [27], [28]; CO
2
-air, N
2
-air, R12-air,
R134a-air [39]; CO
2
-air, N
2
-air, Steam-air
[24]; MeBr-air [24].
Flammability of Ethylene Oxide &
Water Mixtures
In closed systems such as sewers, 100 to 1
water to EO dilution ratios (vol/vol) may be
required to produce a mixture that will not
support combustion. In open systems, such as
around an atmospheric spill, water/EO mix-
tures can support combustion if the water/EO
ratio is less than 22 to 1.
Decomposition
Pure EO vapor or EO vapor mixed with air or
inert gases can decompose explosively. The
decomposition reaction is expressed by the
following equation:
EO > CO + CH
4
+ 1312 BTU/lb
The reaction can also produce ethane, ethylene,
hydrogen, carbon and acetaldehyde [10,17].
At atmospheric pressure, thermal decomposi-
tion of pure EO vapor occurs at 1040F
(560C). This is the number most frequently
cited as the decomposition temperature.
However, lower gaseous EO decomposition
temperatures have been reported indicating
that decomposition temperature is affected by
pressure, surface characteristics, volume, and
geometry. EO can also ignite and decompose
explosively at pressures below atmospheric,
down to a pressure of around 4.8-5.8 psia, but
at greater than 1040F (560C).
Once the decomposition reaction has been
initiated, it can be propagated from the
ignition source through the gas phase as a
flame and, under certain conditions, may be
explosive. It is important to understand that
this reaction can occur in the absence of air
or oxygen.
High pressure can be generated by decomposi-
tion of EO. The maximum theoretical
explosive pressure is about 10 times the initial
pressure, but can increase to 20 times the
initial pressure if liquid EO is present. This
phenomenon occurs because liquid EO evapo-
rates and participates in the decomposition
reactions which take place in the vapor
phase [15].
Mixtures of EO with nitrogen, carbon dioxide
and methane will not decompose over certain
concentration ranges. Thus, vapor decomposi-
tion can be prevented by dilution with a
suitable inert gas. Nitrogen is usually the gas
of choice, but methane and other diluents
have been used. The dilution quantity depends
on temperature, pressure, and the expected
ignition source and duration [9]. The most
thorough discussion of the EO decomposition
process is presented in [17]. The minimum
total pressure for inert blanketing is important
[9,10], and section 6.5 presents information
relevant to the inerting of EO in storage and
handling systems. For inerting of vapor spaces
of reactors using EO as feeds or reagents, the
system is quite complex and beyond the scope
of this publication.
EO liquid mists will decompose explosively
similarly to the vapor. The decomposition of
this two-phase mixture yields greater pressures
and rates of pressure rise than the vapor alone
[17]. Liquid EO can participate in a decompo-
sition that starts in the vapor phase. Explosion
of liquid EO, initiated by a strong ignition
source within the liquid, was first described in
1980. It is thought that the ignition source
vaporizes liquid EO, and the decomposition
reaction takes place in the gas phase.
Properties of Ethylene Oxide
2-6
0
20
40
60
80
100
Flammable Region
1/2 atm
3 atm
FIGURE 2.4: Effects of Pressure on Flammable Region
of Ethylene Oxide/Nitrogen/Air Mixtures
N
i
t
r
o
g
e
n

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
E
O

C
o
n
c
e
n
t
r
a
t
i
o
n

(
%

V
o
l
)
Air Concentration (% Vol)
100 60 80 20 40 0
100
80
40
60
0
20
Exothermic Reactions with Rust
Following a major industrial incident, it was
discovered that EO vapor in contact with high
surface area metal oxides, such as the gamma
form of iron oxide, can undergo exothermic
reactions (disproportionation) that can raise
local temperatures above the decomposition
temperature of EO [42].
The disproportionation reaction has been rep-
resented by the following equation:
6 EO => 5C
2
H
4
+ 2CO
2
+ 2H
2
O
But depending on the reaction conditions, the
ratio of C
2
H
4
to CO
2
has been found to vary
from 1.5 to 2.5.
This reaction can be initiated at significantly
lower temperatures than thermal decomposi-
tion. In the case of the industrial incident
noted above, the reaction occurred:
On the tubes of a distillation column
reboiler,
In the presence of a deposit of high
surface area rust imbedded in an EO
polymer matrix, and
During a period when flow through the
reboiler was reduced by a process upset.
It was concluded that loss of reboiler circula-
tion allowed for rapid heat buildup in the
vicinity of the iron oxide/polymer deposit,
resulting in localized temperatures reaching
the EO thermal decomposition temperature.
The result was an explosion that destroyed the
distillation column.
Britton [17] has indicated that rust with very
high surface areas can also initiate EO ignition
at 284F (140C) or below with or without
air present.
Polymerization
EO has a tendency to polymerize. For pure
EO, the reaction is slow at ambient tempera-
tures. The reaction is exothermic, releasing
900 BTU per pound of EO reacted [13].
Britton [17] has reported a rust catalyzed heat
of polymerization of 1102 121 BTU/lb.
The usual catalysts for EO reactions, such as
strong alkali [18], iron oxide (rust) [19], and
other metal oxides catalyze the reaction.
When catalyzed by rust, it is most often a
nuisance, causing line and equipment plug-
ging and off-specification product. However,
the presence of large quantities of loose rust
could pose a significant safety hazard (see dis-
cussion above). Britton [17] also indicated
self-polymerization at 392F (200C) in a
closed, near-adiabatic system, and non-
catalytic conditions.
The condition of metal surfaces is extremely
important in determining the rate of EO poly-
mer formation. It has been reported [19] that
even clean carbon steel catalyzes polymeriza-
tion, although at a much slower rate than
rusty steel. Other factors that affect rate of
polymerization:
Metal surface to volume ratio
Temperature
Equipment residence time
Stainless steel is often the best choice for
materials of construction, especially when the
surface to volume ratio is high. The polymer-
ization reaction has not been found to be
auto-catalytic [43]. That is, the presence of
polymer does not accelerate the polymeriza-
tion process.
Contamination of EO with catalysts such as
KOH or overheating can lead to runaway
polymerization. Reference [18] has a discus-
sion of an EO polymerization (or Poly-
condensation) incident brought about by
contamination of an EO-containing cylinder
with chlorine and alkali. The result was an
accelerating or runaway reaction that ended
with an explosion after about eight hours.
2-7
Table 2.5. Solubilities of poly(ethylene oxide) in various solvents [45]. Solubilities are given in
weight percent. S signifies completely soluble.
Mol Wt 500 600 Mol Wt 3000 - 3700
Solvent T=68F T=122F T=68F T=122F
Water 73 97 62 84
Methanol 48 96 35 S
Acetone 20 S <1 S
Trichloroethylene 50 90 30 80
Heptane 0.5 .01 <.01 <.01
Properties of EO Polymer
Pure EO polymers have been characterized
[44] as clear viscous liquids (molecular weight
less than 600) and as opaque white solids
(higher molecular weight). However, in
industrial settings EO polymer is often dark
brown or black, due to the presence of mag-
netite iron oxide inside the polymer matrix.
Note that the density is significantly higher
than that of EO. This means that polymer
that precipitates inside a storage container
will tend to collect on the bottom.
Solubility of EO polymer in various solvents,
including EO, is a function of molecular
weight of the polymer and temperature. In
general, higher molecular weight polymer is
harder to dissolve. Solubilities of low molecu-
lar weight EO polymer in various solvents are
given above.
Of note is the extremely low solubility in the
non-polar solvent heptane.
Polymer samples from EO processing and
storage equipment have had molecular weights
ranging from a few thousand to over one
million. At the upper end of this range, the
polymer is quite insoluble in solvents and hot
water, and must be removed by physical means.
Static Electricity
Liquid EO is an electrically conductive fluid
and static electricity charges cannot accumu-
late in metal containers using proper bonding
and grounding techniques (see NFPA 77
Static Electricity Guide). Bottom filling is
not required unless there are isolated internal
areas that might accumulate a charge. Static
charge can accumulate in liquid mist produced
as a result of splashing and spraying, and
excessive fill velocities should be avoided to
minimize this effect. {See Eichel [32] for a dis-
cussion of electrostatic calculations.}
Pure EO vapor minimum ignition energy
(MIE) is about 1000 mJ [9]. A typical indi-
vidual can initiate static discharge energy in
the range of 1-50 mJ, and the energy from
ordinary spark plugs is ca. 20-30 mJ [31].
Thus, static energy discharge, in the absence
of air, is not a significant hazard under normal
handling and storage conditions.
Properties of Ethylene Oxide
2-8
Table 2.4 Physical Properties of Pure poly(ethylene oxide) [44]
Molecular Weight Melting Temp. (F) Density (g/cc)
200 -85 (softening) 1.127
600 72 (softening)
1000 102
3400 131 1.204
10,000 145
100,000 150 1.130
4,000,000 150
The presence of even small amounts of air
with EO vapor makes it more sensitive to
ignition. The MIE for EO with air is reduced
to a much lower level (0.06 mJ [9]) and is sub-
ject to ignition by static sparking ignition or
other common ignition sources. {For compar-
ison the MIE for hydrogen is 0.01-0.02 mJ and
that for ethylene is 0.07-0.12 mJ [33].}
2.4 Commercial Chemistry
EO is a very versatile compound, storing con-
siderable energy in its ring structure. Its
reactions proceed mainly via ring opening and
are highly exothermic. Only a few of the
large number of possible reactions are briefly
discussed here. More detailed information
can be found in [8]-[14].
Addition to Compounds with a
Reactive Hydrogen Atom
EO reacts with compounds containing a reactive
hydrogen atom to form a product containing a
hydroxyethyl group:
Examples of XH are: HOH, H
2
NH, HRNH,
R
2
NH, RCOOH, RCONH
2
, HSH, RSH,
ROH, N=CH, and B
2
H
6
(R= alkyl or aryl).
The reaction is accelerated by acids and bases.
All common acids and Lewis acids as well as
zeolites, ion exchangers [29] and aluminum
oxide are effective catalysts. A detailed
discussion of reaction mechanisms and chem-
istry can be found in [12] and [30].
Since the end product of the above reaction
contains at least one hydroxyl group, it can
react successively with additional EO to pro-
duce long chain polyether polymers which are
sometimes called poly-oxyethylene-glycols.
The molecular weight distribution of the
polymers depends on the reaction conditions,
catalysts employed and the ratio of reactants.
Commercially, the most important of this type
of reaction is the reaction with water to pro-
duce ethylene glycols. Over half the total EO
production is used in ethylene glycol produc-
tion. The production of poly(ethylene)
glycols by this route is also of commercial
importance.
When used with starting materials other than
water (e.g., phenols, ammonia, fatty amines,
fatty alcohols, and fatty acids), this reaction,
often referred to as ethoxylation, is used to
produce the bulk of the other commercially
important EO derivatives.
Addition to Double Bonds
EO can add to compounds with double bonds,
e.g., carbon dioxide, to form cyclic products:
EO also adds to other double bond systems,
e.g., to R
2
C=O, SC=S, O
2
S=O, RN=CO, and
OS=O.
Catalytic Isomerization to
Acetaldehyde
Aluminum oxide (Al
2
O
3
), phosphoric acid
and phosphates, iron oxides, and, under cer-
tain conditions, silver, catalyze the
isomerization of EO to acetaldehyde.
XH + H
2
C CH
2
XCH
2
CH
2
OH
O
EO
O=C=O + H
2
C CH
2
H
2
C CH
2
O
C
O
O O
CO
2
EO
=
Ethylene Carbonate
H
2
C CH
2
CH
3
CH
O
EO
O
=
Acetaldehyde
2-9
Properties of Ethylene Oxide
Other Reactions
A highly reactive compound, EO reacts with
many other compounds including: hydrogen
(catalytic reduction to ethanol); hydrogen sul-
fide and mercaptans; Grignard reagents;
halides; hydrogen cyanide; dimethyl ether;
compounds with active methylene or methyne; etc.
2.5 Uses
Products derived from EO have many different
uses. They include:
Monoethylene Glycol: Antifreeze for
engines, production of polyethylene
terephthalate (polyester fibers, film, and
bottles), and heat transfer liquids.
Diethylene Glycol: Polyurethanes, poly-
esters, softeners (cork, glue, casein, and
paper), plasticizers, gas drying, solvents,
and de-icing of aircraft and runways.
Triethylene Glycol: Lacquers, solvents,
plasticizers, gas drying, and humectants
(moisture-retaining agents).
Poly(ethylene) Glycols: Cosmetics,
ointments, pharmaceutical preparations,
lubricants (finishing of textiles, ceramics),
solvents (paints and drugs), and plasticizers
(adhesives and printing inks).
Ethylene Glycol Ethers: Brake fluids,
detergents, solvents (paints and lacquers),
and extractants for SO
2
, H
2
S, CO
2
, and
mercaptans from natural gas and refinery
gas.
Ethanolamine: Chemicals for textile fin-
ishing, cosmetics, soaps, detergents and
natural gas purification.
Ethoxylation products of fatty alcohols,
fatty amines, alkyl phenols, cellulose, and
poly(propylene glycol): Detergents and
surfactants (nonionic), biodegradable
detergents, emulsifiers, and dispersants.
2- 10
Health Effects of Ethylene Oxide
3.1 Overview
A handler of EO should be familiar with the
Occupational Safety and Hygiene Act [1]
standards contained in 29 CFR 1910.1047,
which defines the personnel exposure limits
given below.
EO is regulated by OSHA as a cancer and
reproductive hazard. OSHA had the follow-
ing comment about EO toxicology:
Clinical evidence of adverse effects associated
with the exposure to EtO [Ethylene Oxide] is pre-
sent in the form of increased incidence of cancer in
laboratory animals (leukemia, stomach, brain),
mutation in offspring in animals, and resorptions
and spontaneous abortions in animals and human
populations respectively. Findings in human and
experimental animals exposed to airborne concen-
trations of EtO also indicate damage to the genetic
material (DNA).
The International Agency for Research on
Cancer (IARC), an agency of the World
Health Organization, classifies EO as Class 1
carcinogenic to humans [2]. Section 7 has
additional information on the OSHA standard.
3.2 Short Term Exposure to
Ethylene Oxide
Skin Contact
EO is reactive, and direct contact should be
avoided. Liquid EO can cause freezing of the
skin by evaporative cooling. It is also highly
irritating to the eyes and skin, and even dilute
solutions can cause blistering or severe dam-
age to the skin or eyes. EO easily penetrates
cloth, leather, and some types of rubber, and
can produce blistering if clothing or footwear
contaminated with EO is not removed. See
Figure 7.1 in section 7.3.
Inhalation
EO has a high odor threshold (>250 ppm),
and sense of smell does not provide adequate
protection against its toxic effects. The effects
of exposure are concentration and time
dependent. Concentrations of several hun-
dred ppm may be tolerated for a few minutes
without significant immediate health effects.
Similar concentrations may cause severe
injury, especially if inhaled for longer periods.
The rat LC
50
(concentration to kill 50% of
animals) was 5000 ppm for a 1 hr exposure,
and about 1460 ppm for a 4 hr exposure [3].
Overexposure of animals and humans to EO
vapor will cause irritation of exposed surfaces,
including eyes, skin, nose, throat and lungs. If
the lungs are affected, secondary infections
may lead to pneumonia. Short-term overex-
posures may also affect the central nervous
system, leading to symptoms such as drowsi-
ness, disorientation, nausea, and vomiting.
Convulsions and limb weakness may also
occur. These symptoms may be expected to
reverse within a few days after cessation of
acute exposure. The exposure levels that
could cause such effects are believed to be far
above current occupational standards.
IDLH
The National Institute for Occupational
Safety and Health has quantified exposures to
approximately 400 toxic chemicals which
could be Immediately Dangerous to Life and
Health (IDLH). The IDLH exposure value
for EO is 800 ppm.
The official definition of IDLH is given in 30
CFR 11.3. The IDLH concentration repre-
sents an estimate of the maximum concen-
tration of a substance in air from which
healthy workers can escape without loss of life
or irreversible health effects under conditions
of a maximum 30 minute exposure time.
For more discussion of IDLH, see reference [4].
Exposure Limits
Action Level 0.5 ppm (8hr. TWA*)
Permissible
Exposure Limit 1 ppm (8hr. TWA)
Excursion Limit 5 ppm
*Time Weighted Average
3- 1
ERPG
The American Industrial Hygiene
Association (AIHA) has recommended
Emergency Response Planning Guidelines
(ERPGs). AIHA has recommended an
ERPG-3 of 500 ppm, which is the maximum
airborne concentration below which it is
believed nearly all individuals could be exposed
for up to one hour without experiencing or
developing life threatening health effects.
The ERPG-2 of 50 ppm is the maximum air-
borne concentration below which it is
believed nearly all individuals could be
exposed for up to one hour without experienc-
ing or developing serious health effects or
symptoms that could impair an individuals
ability to take protective action.
There is no specified ERPG-1, the maximum
concentration below which it is believed
nearly all individuals could be exposed for up
to one hour without experiencing other than
mild, transient effects or without perceiving a
clearly defined objectionable odor.
3.3 Long Term Exposure to
Ethylene Oxide
General
Long term overexposure is generally associ-
ated with lower air concentrations than those
associated with the acute effects noted in
section 3.2.
Repeated dermal exposure to EO, or materials
treated with EO, may lead to skin sensitiza-
tion (allergic) reactions. Repeated exposure to
high inhalation concentrations may result in
respiratory sensitization (asthmatic) symptoms.
There are several other important effects to
consider in the case of repeated exposures.
These relate to the central nervous system,
reproduction, genetic effects, and cancer.
There is also a possible association with
cataract formation [3].
Neurological Effects
The neurological effects of long-term overex-
posure are similar to those of acute short-term
exposure in humans. Many of the effects may
be non-specific, including headaches, nausea,
lethargy, numbness, and memory loss. There
may also be a reduced sense of smell and/or
taste, and muscle weakness, particularly in the
legs. If these symptoms occur it is likely they
would have been caused by exposures much
higher than the permissible exposure limit
(PEL). The effects of EO on the nervous sys-
tem are regarded as reversible. No neurotoxic
effects were reported in rats or monkeys
exposed to high inhalation concentrations
of EO [5].
Reproductive Effects
Experimental studies have shown reproductive
effects in rodents exposed to EO. Male and
female rats were exposed by inhalation to EO
at 10, 33, or 100 ppm for 10 weeks and then
mated. A decrease in the number and weight
of offspring were noted at the highest two con-
centrations. There was no apparent effect on
the mothers or the development of the pups
during lactation [6]. In other studies in mice,
repeated exposure of the male alone to EO
concentrations of 150 ppm and above resulted
in a decrease number of live offspring, suggest-
ing a mutagenic effect on sperm [7][8].
The effects of EO on fetal development have
been examined in the offspring of rats exposed
to 10, 33, or 100 ppm during pregnancy [9].
The only reported effect on the mother or off-
spring was decreased weight of the pups at the
highest concentration. There were no malfor-
mations or other indication that EO was a
developmental toxicant.
Repeated exposures of pregnant rats to higher
concentrations for shorter times, intended to
mimic EO exposure during sterilizer use, did
not enhance the effect of decreased pup
weight, nor produce malformations [10].
There have been a few epidemiological reports
of increased spontaneous abortions in pregnant
hospital or dental sterilizer workers exposed for
Health Effects of Ethylene Oxide
3- 2
short times to relatively high EO concentrations
[1]. However, methodological questions have
raised doubts about the conclusions drawn in
these studies [12].
Genetic Effects
Because EO is reactive, it is capable of directly
combining with proteins and DNA when it is
absorbed into the body. Since EO reacts
directly with DNA, it can be anticipated to
cause genetic effects when the exposure is suf-
ficiently high [13].
The genetic effects of EO have been examined
in both normal body cells (i.e., cells not
involved in reproduction) and reproductive
tissue. The effects of EO on white blood cells
have been studied and evaluations made on
both laboratory animals and exposed workers.
White blood cells were used because of ease of
obtaining and culturing samples. It has been
concluded from these studies that genetic
changes (sister chromatid exchanges) may
occur in workers exposed long-term to concen-
trations of 10 ppm or higher. It should be
noted that these effects have not been associ-
ated with any specific disease, but are often
used as an indication of exposure to EO.
The impact of EO on male and female repro-
ductive cells has been the subject of much
research. In experiments on mice, it has been
shown that exposure of males to high levels of
EO causes mutations in the reproductive cells
involved in the development of spermatozoa.
These mutations are transmitted to offspring
and may result in failure of fetuses to develop
to term (dominant lethal effect). This study
and others, primarily on mice, have been used
to evaluate the genetic risk for exposed
humans [14]. At the current occupational
exposure limits (PELs), the risk of heritable
effects is considered to be very low [15].
Carcinogenic Effects
The ability of EO to cause cancer has been
assessed in three animal inhalation studies, and
in many studies of occupationally exposed
workers. Based primarily on animal data and
on cytogenetic changes in exposed workers, the
International Agency for Research in Cancer
recently classified EO as a known human
carcinogen [2].
Two animal inhalation studies were conducted
in rats, and one in mice. In each study there
was a dose-related increase in the type and
number of tumors, although it is uncertain if
these findings can predict quantitative risk of
cancer in man [16].
The epidemiological studies of EO-induced
cancer in workers has been recently reviewed
[17]. About 30,000 workers were reviewed in
this study. The authors concluded that
although the current data do not provide con-
sistent and convincing evidence that EO
causes leukemia or non-Hodgkins lymphoma,
the issues are not resolved and await further
studies of exposed populations. No association
of EO exposure with any other tumor sites was
indicated in this review. Follow-up studies are
currently being funded by the Ethylene Oxide
Industry Council of the Chemical
Manufacturers Association. To date, mortality
from cancer among workers exposed to EO has
been studied in 12 distinct groups that include
over 33,000 individuals. An objective conclu-
sion from these studies is that EO does not
cause an increased risk in mortality, of cancer
overall, or cancer of the brain, stomach or
pancreas that was reported in some animal or
isolated human studies. The evidence relating
to added risk from leukemias and lymphomas is
inconclusive, although workers in the epidemi-
ologic studies were exposed at concentrations
far higher than prevailing occupational exposures.
3- 3
4.1 Summary
Ethylene oxide is not persistent in the envi-
ronment because it is reactive and degrades by
biotic and abiotic processes. It has been con-
cluded that between biochemical oxidation,
reactivity, volatilization, and dilution, toxic
levels of ethylene oxide are unlikely to be pre-
sent except in a very localized incident area
[1]. Ethylene oxide has been shown to have
low to moderate aquatic toxicity, and as a
result, does not present a significant risk to the
environment.
4.2 Properties of Ethylene Oxide
in the Environment
Since it is reactive, EO does not persist indefi-
nitely in the environment. The processes of
hydrolysis, photolysis, volatilization, and
biodegradation all result in its removal. In
addition, ethylene oxide does not readily
absorb into sediments or soils and does not
bioconcentrate. A summary of environmen-
tally relevant physical properties is given in
Table 4.1.
Hydrolysis
Chemical hydrolysis is a major removal
process. An impression exists that EO in
water is quickly converted to ethylene glycol.
However, conversion to glycols at ambient
temperatures requires weeks for completion.
Figure 4.1: Ethylene Oxide Hydrolysis,
shows conversion data for EO in fresh water
(half-life of 14 days) [1]. In 3% salt water,
hydrolysis is somewhat faster (half-life of 9
days) [1]. The rate of EO hydrolysis is both
pH and temperature dependent. Acidic con-
ditions can have a large positive effect on
hydrolysis rates [7]. The data for ethylene
oxide indicates that water temperature will
probably have a greater effect on half-life than
expected pH differences in natural waters [1].
The hydrolysis product, ethylene glycol, is
biodegraded rapidly in the aquatic
environment [8].
Volatilization
Because of its volatility, ethylene oxide has a
tendency to transfer from water or soil to the
air. The Henrys Law Constant is 1.4 x 10
-4
atm-m
3
/mole [1]. It has been shown that the
transfer rate of ethylene oxide from natural
waters is about 0.36 times that of oxygen
under the same conditions [1]. A 4-hour aera-
tion test resulted in 100% removal from water
[9], and the volatilization half-lives for
removal from a model river and model lake
are 5.9 hours and 3.8 days, respectively [10].
Persistence in Air
Earlier studies suggested that EO is not
persistent in air due to washout by rain [1] and
degradation by chemical processes [11].
However, more recent work has indicated that
EO was not readily deposited by rain [12],
[13], and the dominant chemical removal
process is the reaction with the hydroxyl radi-
cal. In a study of the reactivity/volatility
classification of organic chemicals, ethylene
Environmental
Table 4.1: Environmentally relevant parameters.
Parameter Units Value Reference
Water solubility mg/L miscible [2]
Vapor pressure at 20C mm Hg 1095 [2]
Henrys Law Constant at 20 C atm-m
3
/mol 1.4 x 10
- 4
[1]
Octanol -water partition -- - 0.30 [3]
coefficient (log K
OW
)
Soil - sediment partition -- - 0.56 [4][5]
coefficient (K
OC
)(a)
Bioconcentration factor (BCF)(b) -- 0.35 [4][5]
Theoretical oxygen demand (ThOD) g O
2
/g EO 1.82 [6]
(a) Calculated using log K
OC
= 0.544 log K
OW
+ 1.377 ([4], [5])
(b) Calculated using log BCF = 0.76 log K
OW
0.23 ([4], [5])
4- 1
Table 4.2: Ethylene oxide biological degradation data.
Process Results Comments Reference
aerobic 5- d BOD = 20% standard BOD test [9]
10- d BOD = 62%
20- d BOD = 70%
aerobic 5- d BOD = 3% standard BOD test [20]
aerobic 20- d BOD = 52% lightly seeded BOD test [1]
99% conversion
half-life
T
i
m
e
,

H
o
u
r
s
0.1
1
10
100
1000
10000
100000
FIGURE 4.1:
Temperature, F
0 120 200 240 160 40 80
Ethylene Oxide Hydrolysis of Dilute, Neutral Solutions
4- 2
oxide was classified as a Class I chemical, i.e.,
sufficiently unreactive in the atmosphere so
that it may not participate in photochemical
smog formation [14]. The atmospheric half-
life is estimated to be approximately 200-300
days from OH reaction rate [13], while other
reports have indicated atmospheric half-lives
ranging from 38 to 380 days without account-
ing for other removal mechanisms [15], [16].
Biodegradation
A series of biodegradation experiments (bio-
logical oxygen demand (BOD) tests) have
been conducted and are summarized in Table
4.2. These results indicate the ethylene oxide
is rapidly and extensively biodegraded under
aerobic conditions. More rapid biodegrada-
tion is expected in acclimated systems [17],
[18]. Thus, ethylene oxide will biodegrade in
aerobic systems such as rivers, lakes, and
activated sludge units. However, high con-
centrations of EO may cause inhibition of
bacterial respiration in activated sludge units.
The IC
50
(concentration that inhibited
bacterial growth by 50%) in an activated
sludge test (non-acclimated) was in the range
of 10-100 mg/L [1]. It should be noted that
EO is commonly used as a sterilizing agent
because of its bactericidal activity [19].
In testing of a full-scale chemical plant acti-
vated sludge unit, ethylene oxide was shown
to rapidly biodegrade to non-detectable levels
[18]. Measured ethylene oxide biodegradation
kinetics were determined in this study and
were successfully used to predict the measured
activated sludge unit EO emissions [18].
4.3 Ecotoxicological Effects
Ethylene oxide aquatic toxicity studies have
been conducted using fish and crustaceans.
The results indicate that ethylene oxide has
low to moderate aquatic toxicity (Table 4.3),
with toxicity measurements (LC
50
in acute
tests) ranging from 57 to 274 mg/L for fish and
137 to 1000 mg/L for crustaceans.
The effect of ethylene oxide on the growth
and development of plants has also been
investigated. Heck and Pires [22] reported
that atmospheric concentrations of 10 ppm
showed no effects on plants after seven days of
exposure but concentrations as high as 1000
ppm in air caused death for all of the five
plant species tested. Ethylene oxide is also
reported to affect germination of seeds and
show mutagenic activity in plants [19].
4.4 Evaluation of Ethylene Oxide
Spills
Ethylene Oxide in Soil
Should EO come in contact with soil, much
of the material will be lost to evaporation and
the balance will infiltrate the ground. Down-
ward penetration of liquid toward the
groundwater table may cause environmental
concerns as hydrolysis to ethylene glycol is
relatively slow (see above). However, the
ethylene glycol formed from hydrolysis biode-
grades rapidly (0.2 to 0.9 day half-life) [23].
After a spill, evaporation will continue within
the soil, but at a reduced rate. Dilution of an
EO release with water will increase the viscos-
ity of the resulting mixture and will have the
net effect of reducing the speed of downward
movement in the soil. If the soil surface is sat-
urated with moisture at the time of the
release, as might be the case after a rain, the
EO will tend to run off or pond and eventu-
ally evaporate. Calculation methodology
(with examples) for evaluation of subsurface
behavior of EO in several types of soils has
been documented in the EO EnviroTIP
manuals developed by the Canadian
Environmental Protection Service [19].
Ethylene Oxide in Water Systems
When spilled on water, ethylene oxide will
volatilize and, at the same time, spread on the
surface and mix with the water. EO
EnviroTIP manuals [19] also document
methodology to evaluate both spreading and
mixing components of an EO release to water.
Environmental
Species Results Comments Reference
Fathead minnow Maximum safe no effect [9]
concentration (96-h) concentration
= 41 mg/L
Fathead minnow 96-h LC
50
= 57 mg/L static; fresh water [9]
Fathead minnow 24-h LC
50
= 86, 90, static; fresh water [1]
274 mg/L
48-h LC
50
= 89 mg/L
96-h LC
50
= 84 mg/L
Goldfish 24-h LC
50
= 90 mg/L static; fresh water [21]
Daphnia magna 24-h LC
50
= 260, static; fresh water [1]
270, >300 mg/L
48-h LC
50
= 137,
200, 300 mg/L
Brine shrimp 24-h LC
50
= 350, static; salt water [1]
570, >500 mg/L
48-h LC
50
= 490,
>500, 1000 mg/L
Table includes multiple results from separate tests.
Table 4.3: Ethylene oxide aquatic toxicity data.
4- 3
Ethylene Oxide Dispersion in Air
EO vapor cloud dispersion in air following a
release can be evaluated using computer based
dispersion models available commercially
from a number of sources [24]. Dispersion
estimates can also be made using nomographs
in the EO EnviroTIP manual [19]. Analytical
predictive models have been developed by the
EPA for hazardous waste treatment, storage
and disposal facilities [25], and these can be
used to estimate EO emissions to air. Vapor
emissions (including, but not limited to EO)
from contained spills, either on land or water
surfaces can also be predicted with methodol-
ogy developed by Wu and Schroy [26].
4.5 Fugitive Emissions
A 1983 study, funded by the EPA, described a
methodology for estimating fugitive emissions
of volatile organic compounds (VOC) on the
basis of numbers of valves, flanges, etc., and
concentrations of VOC in equipment. The
methodology included use of SOCMI
(Synthetic Organic Chemical Manufacturing
Industries) emission factors for estimating
fugitive emissions, and was general for VOCs.
The 1983 methodology was significantly
refined in a 1988 study sponsored by the
Chemical Manufacturers Association (CMA)
in cooperation with the United States EPA.
New correlation equations were developed for
estimating fugitive emissions that are specific
for manufacturing facilities handling EO. In
general, CMA emission factors resulted in
lower emissions estimates than the 1983
SOCMI emission factors.
The 1993 US EPA Protocol for Equipment
Leak Emission Estimates provides two meth-
ods for estimating VOC emissions. One
option is updated SOCMI emission factors,
which were revised from the 1983 factors
based on the 1988 CMA study. These factors
will yield lower estimates than either the 1983
or 1988 correlations. As with the 1983
SOCMI factors, a reduction in estimated
emissions is allowed if the facility has a Leak
Detection and Repair (LDAR) program. This
estimation option may be used for emission
inventories or permit applications.
The other option in the 1993 Protocol [27]
uses field leak concentration data collected for
compliance with US EPA leak detection and
repair (LDAR) requirements to calculate fugi-
tive emissions. If the number of components
found to be leaking is small, using the Fugitive
Emissions Correlation Equations may result in
even lower calculated fugitive emissions.
These correlations allow calculation of an
emission rate for each component (flange,
pump seal, etc.) using the actual reading taken
in the field. Many commercially available
data bases developed to document LDAR
compliance can also calculate the fugitive
emissions based on the data collected.
Fugitive emission rates calculated in this man-
ner may be used for annual emissions
inventory reporting, but not for permit
applications.
4- 4
Overview of Hazards
5.1 Introduction
Over the past 50 years, there have been many
incidents in both EO production plants and
EO consuming plants [1] resulting in major
plant damage, as well as fatalities. There have
also been a significant number of EO trans-
portation incidents.
One of the best ways for the EO user to under-
stand the hazards of EO is to become familiar
with the incidents that have occurred in the
past and their causes. The lessons learned will
help in design of safer plants and development
of procedures for safe operations, mainte-
nance, training and emergency response.
5.2 EO Contamination Incidents
EO is routinely reacted with other chemicals
under controlled conditions to produce com-
mercial products in a safe manner. The fact
that EO is reactive with so many other chemi-
cals and the reactions are highly exothermic
causes contamination to be one of the most
significant hazards of working with EO.
Contamination of pure EO with many other
chemicals, including water, or with waste
materials can lead to uncontrolled reactions
producing large amounts of heat.
Contamination of EO with Aqueous
Ammonia
This incident occurred in 1962 at an EO pro-
duction and derivatives plant. An EO storage
tank containing 25 tons of EO was contami-
nated with aqueous ammonia due to back-flow
from an ethanolamines unit. A rapid reaction
in the tank between the EO and the ammonia
resulted in over-pressure and rupture of the
tank, followed by an EO vapor cloud explo-
sion. (Figures 5.1, 5.2, 5.3) Ignition of the
vapor cloud caused heavy structural damage in
a radius of 500 feet from the blast center. The
explosion resulted in one fatality, three serious
injuries, and 18 less serious injuries. The EO
producers investigation revealed that ammo-
nia entered the EO storage tank by back-
flowing through the EO transfer line. The
ammonia passed through several check valves
and a positive displacement pump (through its
relief valve) to get to the EO tank [2,3] . 5- 1
Figure 5.1 Blast center EO tanks no
longer visible after explosion
Figure 5.2 Aerial view of the plant showing
overall damage
Figure 5.3 Plant laboratory after EO vapor
cloud explosion 300 feet away
Railcar Explosion Due to Reaction
Between Residual EO and Cleaning
Water
An EO railcar was sent to a contractor for
cleaning. It contained a heel of a few thou-
sand gallons of EO. The contractor pumped
brackish water into the car and left it in a rail
yard overnight. During the night it exploded,
causing significant damage to other railcars in
the rail yard. (Figures 5.4, 5.5, 5.6) The EO
producers investigation revealed that a major
contributing factor to this incident was the
fact that the water was added slowly to the
railcar. The EO and water formed two dis-
tinct layers in the railcar due to the difference
in density and inadequate mixing. Due to the
layering, there was an interface between a
high concentration of EO and a high concen-
tration of water. This resulted in a much
higher reaction rate than would have occurred
if the EO and water had been well mixed.
Contaminants in the brackish water may have
also contributed to the high reaction rate.
The subsequent reaction generated a high
temperature and pressure, resulting in rupture
of the car [4].
EO Railcar Contamination with
Bentonite Clay
A railcar was returned to an EO producers
plant after cleaning by a contractor.
Unknown to the EO producer, the cleaning
contractor had put bentonite clay (a drying
agent) in the car, to reduce rust formation.
When the car was received at the plant, the
clay was not removed. During loading with
EO, a fire occurred in the dome of the railcar.
Reaction between the bentonite clay and EO
caused an internal ignition and release of
burning EO vapor through the cars safety
relief valve. The fire was extinguished with
water, but re-flashed. It was finally extin-
guished with dry chemical.
5- 2
Figure 5.4 Remnants of railcar after EO
explosion caused by contamination
Figure 5.5 Remnants of railcar after EO
explosion caused by contamination
Figure 5.6 Damage to other railcars due to
the EO railcar explosion
Contamination of Railcar with
Ammonia
A European EO producer shipped an EO rail-
car to a customer. The railcar was delivered to
the wrong plant and the workers at the receiv-
ing plant thought the car contained
anhydrous ammonia. They attempted to off-
load the EO into an anhydrous ammonia
tank. The ammonia tank was at a signifi-
cantly higher pressure than the pressure on
the EO railcar. During the attempt to offload
the EO, a check valve leaked and allowed a
small amount of ammonia to back-flow into
the EO railcar. When the workers at the
plant discovered that the car was delivered by
mistake, the unloading operation was stopped
and the car containing the contaminated EO
was dispatched on to its proper destination,
300 km away. The railcar car exploded in the
middle of the night on a rail siding at the edge
of the plant. The explosion caused major
damage over a 300-meter radius and broke
windows up to 5 km away. (Figure 5.7)
Explosion of Railcar Containing EO
Washwater
An EO producer in the US washed an EO
ship loading line and an EO storage sphere
with river water, and then stored the EO con-
taminated water in a 22,500 gallon railcar.
The railcar contained 8000 gallons of EO and
5200 gallons of washwater. The car was
loaded at 63F and padded with nitrogen at 35
psig. The railcar sat on a siding for 23 days,
and exploded on December 27, 1973. Prior to
the explosion, the tankcars relief valve lifted,
and the immediate area was evacuated. When
the car exploded, there was a large fireball and
the explosion formed a crater. The adjacent
epoxide plant was demolished. There were 28
people with minor injuries, but no fatalities.
5.3 Formation of Ethylene Oxide
Vapor Clouds
Release of EO vapors can result in vapor cloud
ignition. Such incidents can be extremely
destructive.
Ethoxylation Plant Explosion
The contents of an ethoxylation reactor were
pumped to a neutralization vessel about one
half-hour before completion of all the reac-
tion steps. The neutralization vessel was
located indoors. The material was pumped to
the vessel at a temperature of approximately
390F. It contained 100 to 150 lbs. of unre-
Overview of Hazards
5- 3
Figure 5.7 Remnants of railcar after EO explosion caused by contamination with ammonia.
acted EO. The EO vaporized and escaped
from the vessel rapidly and mixed with the air
in the building. An explosion occurred when
an operator entered the building to turn on
the ventilation system. The explosion killed
the operator that was entering the building,
injured two other operators, and completely
destroyed the building housing the ethoxyla-
tion reactor and the neutralization vessel.
Nearby buildings sustained extensive damage.
5.4 EO Decomposition Incidents
One of the most hazardous properties of EO is
the fact that it will decompose at a tempera-
ture around 1040 F. The incidents listed
below illustrate the most common causes of
EO decomposition incidents.
EO Decomposition Incidents Caused
by External Fires
An external fire is one of the most hazardous
situations that can occur in an EO plant
because of the potential for EO decomposi-
tion. Even with good water spray systems and
well-insulated equipment, flame impingement
from an external fire can increase piping and
vessel wall temperatures to EO decomposition
temperature in a short time period. If this
happens, an internal explosion can occur.
The following are examples of major incidents
that were caused by an external fire.
Fire Around Distillation Column
An EO producer in the US had a rupture
of an EO compressor cylinder. This
resulted in a large fire, which engulfed the
EO distillation column. The resulting
temperature increase on the surface of the
column and in the contained EO resulted
in an internal explosion and significant
damage.
Flange Fire while Plant was Down
A European EO producer experienced a
flange leak in the EO distillation section.
The plant had been shut down, but still
contained an inventory of EO. The flange
leak resulted in a fire and the flame
impinged on a process line containing EO.
The heat caused an EO decomposition
reaction to be initiated in the line. The
decomposition propagated down the line
and into a distillation column. The col-
umn head was torn off and thrown about
100 feet. Large and small parts of the
column jacket were scattered over a 2000-
foot radius. Only 7 minutes elapsed
between the start of the unit fire and the
column explosion.
Pump Seal Leak Fire
An EO pump seal leak is always a signifi-
cant incident because of personnel
exposure concerns. However, if a pump
seal leak ignites, the results can be cata-
strophic. A European EO production
plant had an EO pump seal leak that was
ignited by contact with hot pump parts.
The flame from the pump seal fire
impinged on an uninsulated minimum
flow return line, causing evaporation of
the EO in that line. Continued heat
input from the flame impingement
resulted in a decomposition in the mini-
mum flow line. The decomposition
reaction propagated into the EO purifica-
tion column reflux drum, where an
explosion occurred. The reflux drum and
its associated distillation column were
destroyed. This incident resulted in four
fatalities. The plant was heavily damaged
and out of operation for four months.
5- 4
EO Decomposition Incidents Caused
by Mechanical Equipment
Important concerns regarding pumps and
compressors in EO service are 1) the potential
for high temperatures if mechanical energy is
not dissipated and 2) the potential for a fire
due to seal leaks. A good example of failure to
remove mechanical energy is a blocked pump
discharge. The two incidents described here
are good examples of the results of operating
an EO pump deadheaded. The pump seal
leak fire described on the previous page is a
good example of the potential consequences
of a seal leak fire.
Decomposition in Reflux Pump
Propagates to Reflux Drum and
Tower
A European EO producer had been hav-
ing problems with the EO purification
column reflux pump over-speeding. There
were also instrumentation problems with
the level controller on the reflux drum,
and the incident was triggered by the
reflux control valve failing closed. The
reflux pump operated deadheaded against
the level control valve, causing tempera-
ture in the pump to rise, vaporizing EO
and causing a decomposition reaction.
The decomposition propagated through
the pump suction line into the reflux ves-
sel where an explosion occurred. Shortly
afterward the EO purification column
exploded. This explosion resulted in four
fatalities. The plant was heavily damaged
and out of operation for four months [5].
EO Decomposition in Blocked-in
Pump
A US EO producer used high-speed cen-
trifugal pumps to feed EO to two ethylene
glycol units. The plant had a common
spare feed pump for the two glycol units.
The spare pump was typically kept cleared
of EO, pressured up with 200 psig nitrogen
and left with the suction and double dis-
charge valves blocked in. A small amount
of EO leaked through two blocked dis-
charge valves into the pump. An
electrical system malfunction caused the
high-speed centrifugal pumps electric
motor to start. The pump ran blocked in
for approximately 10 minutes until the
seal area of the pump reached EO decom-
position temperature and the pump
Overview of Hazards
Figure 5.8 High speed centrifugal pump launched by decompostion of 0.6 lb. of EO
5-5
exploded. The decomposition of the 0.6
lb. of EO generated over 450,000 pounds
of force and caused the failure of twelve,
3
4" stainless steel nuts and bolts. (Figure
5.8) The upper part of the vertical cen-
trifugal pump and the motor (approxi-
mately 1000 lb.) were launched 60 feet in
the air. The pump and motor landed on
the discharge piping of another EO feed
pump that was operating at 750 psig,
pumping 80 gpm of EO. Fortunately the
piping did not fail. (Figure 5.9)
EO Decomposition Incidents Caused
by Leaks
Under Insulation
High temperatures can develop in EO
leaking under porous insulation due to
reaction of EO in contact with the insula-
tion. Types of porous insulation subject to
this problem include mineral wool,
asbestos, fiberglass, calcium silicate,
magnesium silicate, and others. Porous
insulation can soak up and retain water
from the environment, thereby providing
a large surface area for EO/water contact.
In addition, it has also been shown that
many types of insulation catalyze reactions
of EO. These reactions all produce heat,
the dissipation of which is inhibited by
the insulation itself. This can result in a
hot spot on the wall of the vessel, which
can trigger a decomposition reaction.
Since the incidents discussed below,
industry has largely converted to non-
porous insulation such as cellular glass.
This reduces the potential for hot spots
and provides a degree of protection from
overheating due to fire. See section 6.3
for a fuller discussion of insulation.
EO Leak at an Insulated Manway
Flange Results in Tower Explosion
In 1987, a European EO producer had a
catastrophic explosion of their EO purifi-
cation column. The damage to the plant
was very extensive. Investigation after the
incident revealed that a manhole flange
leak under mineral wool insulation on the
EO distillation column resulted in an
external hot spot which caused an EO
decomposition inside the tower. (Figure
5.10, 5.11, 5.12, 5.13)
Figure 5.9 Motor landed on operating EO pump discharge line
5- 6
5-7
Figure 5.10 EO distillation column reboiler after explosion
Overview of Hazards
Figure 5.11 Aerial view of the site showing the extent of the damage
5- 8
Figure 5.12 Remnants of the base of the EO distillation column after the explosion.
The column is gone.
Figure 5.13 Piece of the EO distillation column wall that was turned inside out by
the explosion
EO Leak Under Insulation Results in
Tower Explosion
In 1989, another European EO producer
had a catastrophic explosion of their EO
purification column. A crack developed
where a pipe was attached to the wall of
an EO distillation tower. The crack
allowed EO to leak into mineral wool
insulation. EO reacted with water in the
insulation to produce polyglycols. When
portions of the insulation and insulation
jacketing were removed for maintenance,
air flowed into and under the insulation,
causing rapid oxidation of the polyglycols,
producing a high temperature. The insula-
tion prevented dissipation of the heat, and
the reaction in the insulation caused the
wall temperature of the EO distillation
tower to reach EO decomposition
temperature. The resulting internal
decomposition reaction caused vessel fail-
ure. Damage to the plant was severe,
requiring more than a year for rebuilding.
EO Decomposition Caused by Reaction
in Column Reboiler
EO Re-distillation Column Explosion
An EO manufacturer experienced an
explosion in an EO re-distillation column.
(Figure 5.14) The explosion appeared to
have been initiated at the top of the
reboiler. There was one fatality and the
plant was out of service for more than one
year [6].
After the incident, the EO producers
research identified a previously unknown
reaction of EO: disproportionation (see
section 2.3). This reaction can be initi-
ated at significantly lower temperatures
than thermal decomposition. In the case
of this incident, the reaction occurred
On the tubes of a distillation column
reboiler,
In the presence of a deposit of high
surface area rust imbedded in an EO
polymer matrix, and
During a period when flow through
the reboiler was reduced by a process
upset.
It was concluded that loss of reboiler cir-
culation allowed for rapid heat buildup in
the vicinity of the iron oxide/polymer
deposit, resulting in localized temperatures
reaching the EO thermal decomposition
temperature. The result was an explosion
that destroyed the distillation column.
EO Decomposition Incident Caused
by Catalyst Residue in the Vapor
Space of an Ethoxylation Reactor
An ethoxylation reactor exploded during nor-
mal operation, while EO was being fed to the
reactor. During the investigation of the
explosion, pieces of the reactor head were
found that had a heavy buildup of potassium
hydroxide catalyst on the metal. A liquid
stream containing KOH was added at the top
of the reactor, and a KOH residue had built up
on the inside of the head. The KOH cat-
alyzed a reaction of the EO in the vapor space
of the reactor driving the temperature in
localized areas of the reactor head to the
decomposition temperature and the vapor
space decomposed explosively. The vapor
space was not inerted with nitrogen.
Overview of Hazards
Figure 5.14 Scene of EO re-distillation tower
explosion. EO re-distillation tower is gone and
adjacent tower is damaged and leaning.
5-9
5.5 EO Transportation Incidents
In both of the following transportation inci-
dents an EO railcar was punctured and a fire
resulted. In one incident the emergency
responders controlled the process of burning
off the EO. In the other incident, injuries
were prevented by evacuation.
EO Railcar Fire
A railcar of EO was punctured in a rail acci-
dent and the leak ignited. Three unmanned
fire monitors were set up to limit the temper-
ature increase in the car and to reduce the
likelihood of a hot spot in the car shell.
Nitrogen was fed into the car through a hose
from portable nitrogen bottles to maintain of
an inert atmosphere inside the car. A 1.5
firewater hose was also connected to allow
flooding of the cars interior, should it
become necessary. The fire was allowed to
burn until all liquid EO had been consumed.
When the fire went out, the car was filled
with water as rapidly as possible to cool the
car and to expel unburned EO vapors. No
further damage resulted.
EO Railcar Explosion
A derailment resulted in the puncture of an
EO railcar and a fire. Water was put on the
burning railcar and on an adjacent EO car
that was not leaking. The fire was extin-
guished after about 12 hours. About five
hours after the fire was out, the safety relief
valve on the adjacent car lifted and vapor
from the relief valve caught fire. At this
point, the accident scene was cleared for a
radius of
3
4 mile. After about 55 hours, the
relief valve fire went out for a brief period
and then a violent explosion occurred. A
large piece of the railcar was blown 5,000
feet through the air. The explosion was
attributed to flame propagation back through
the safety relief valve or a hot spot in the
metal near the relief valve that triggered a
decomposition reaction.
5.6 Runaway EO Polymerization
Incidents
Polymerization Incidents in EO
Filters
In 1969, a major US EO producer had an
EO filter explode due to a runaway polymer-
ization. The filter had been left full of EO
and blocked-in. (Figure 5.15)
In May 1998, another US EO producer had
a runaway polymerization in an EO railcar-
loading filter. Circulation through the
loading filter, which normally provides cool-
ing, was stopped for over two days due to
maintenance on other equipment in the EO
tankfarm. The filter elements had not been
changed in 18 months and were highly
loaded with rust. The ambient temperature
at the time of the incident was 100 F. The
combination of the stagnant EO, the high
ambient temperature, and the rust in the fil-
ter elements initiated the polymerization.
The filter case did not rupture, but the tem-
perature in the center of the filter case
exceeded 400 F.
5- 10
Figure 5.15 Filter case after runaway
polymerization
Overview of Hazards
5- 11
5.7 Runaway Reactions in
Ethoxylation Units
Delayed Addition of Catalyst
EO was added to an ethoxylation reactor with
the circulation cooling line blocked. The cir-
culation line was also used for addition of
potassium hydroxide catalyst. In order to con-
tinue feeding EO to the reactor, the operator
had to reset the high temperature EO feed
shutdown. When it was discovered that the
circulation line was blocked, the block valve
was opened to re-establish cooling, but this
action allowed a slug of concentrated KOH
to enter the reactor and come into contact
with EO. Subsequently, the reactor ruptured
explosively. Metal parts and valves were
propelled over a distance of approximately
2300 feet.
Inadvertent Addition of Hydrogen
Peroxide
The reactor in a European ethoxylation unit
suddenly exploded. The incident investiga-
tion revealed that hydrogen peroxide that was
used to bleach the product was inadvertently
added during the EO addition phase of the
operation. The EO reacted with the hydrogen
peroxide and caused the reactor to explode.
5.8 Explosions in EO Abatement
Devices
During 1997, there were explosions at three
plants that use catalytic oxidizers for destruc-
tion of EO in process vents. Each of the
explosions either damaged or destroyed the
catalytic oxidizer. One of the incidents
occurred during the startup testing of the oxi-
dizer. In one of the incidents, there was an
explosion with a fireball, and the oxidizer sys-
tem and the building were destroyed.
6.1 Introduction
The design of facilities for storing, transporting
and processing EO must take into account the
flammability, toxicity, and reactivity characteris-
tics of this material. This summary of EO facility
design issues reflects not only consideration of
its chemical and physical characteristics, but
also the practical experience of industry in deal-
ing with those characteristics. Before using this
section, it is recommended that the reader
review section 5, Overview of Hazards, since
much industry design philosophy has been
developed in response to the incidents summa-
rized in that section.
A significant number of industrial incidents
have been caused by contamination of EO in
storage and shipping containers, followed by
uncontrolled reactions. Much of the design phi-
losophy is based on prevention of
contamination.
Other incidents have been caused by fire
impingement on EO-containing equipment or
reaction of EO leaking under porous insulation.
Designing to mitigate this risk involves careful
selection of insulating materials to provide ade-
quate fire protection of equipment, while
minimizing the insulations reactivity with EO.
Both causes have elevated temperatures inside
equipment to the point where uncontrolled
thermal decomposition occurred.
Risk assessment and hazard analysis are man-
dated by OSHA 29 CFR 1910.119 and should
be an integral part of the initial design of the
facility and should precede modifications to
equipment and procedures.
6.2 Plant Layout & Siting
For plant layout and siting, consider using crite-
ria developed for LPG service in NFPA [1], [2],
[3] and API [4] standards. The user will have to
appropriately modify these standards for EO
service.
Electrical equipment in areas that produce,
store, use, load, or unload EO must conform to
National Electrical Code, Class I, Division 1 or
2, Group B (or Group C if conduit seals comply
with NEC paragraph 501-5(a)).
6.3 Materials of Construction
Because of the reactivity of EO, materials in
contact with EO should be chosen with care.
Metallic Materials
Equipment for storage and handling of EO is
generally fabricated from mild carbon steel or
300 series austenitic stainless steels. Stainless
steels have the advantage of eliminating the
potential for rust, which can catalyze EO poly-
merization.
Austenitic stainless steels such as Type 304 and
Type 316 should be used for small piping, instru-
mentation, and other equipment that cannot be
readily cleaned of rust. They should also be con-
sidered where EO liquid or vapor is likely to
remain stagnant for periods of time.
Carbon steels should be chosen which retain
integrity under the full range of temperatures
encountered in the specific application. Iron
oxide in the form of red hematite or black mag-
netite on internal surfaces of carbon steel
equipment will lead to polymerization of
the EO.
The following metals should not be used
with EO:
Magnesium and magnesium alloys
Mercury
Cast irons (because of low ductility)
Care must be taken with externally insulated
equipment to guard against corrosion under wet
insulation. Wet insulation and metal surfaces
can be caused either by ingress of rainwater or by
condensation of atmospheric moisture on metal
surfaces containing refrigerated EO. Carbon
steel equipment handling EO should be pro-
tected from external corrosion by suitable
coatings. The physical integrity of the coating
and process equipment it protects should be
monitored periodically in accordance with the
plants mechanical integrity program.
6- 1
Design of Facilities
Depending on location and process conditions,
stainless steels can be subject to stress corrosion
from naturally occurring atmospheric chlorides
and may also require external coating.
Non-Metallic Materials
EO rapidly attacks and degrades many of the
organic polymers and elastomers that are nor-
mally used to make O-rings, packing material,
and gaskets. Any polymer or elastomer should
be tested thoroughly to confirm that it is com-
patible with EO before it is used in EO service.
Asbestos and asbestos-filled materials are not
durable in EO service.
Polytetrafluoroethylene (PTFE) is chemically
resistant to EO at temperatures up to 400-500F.
However, virgin PTFE exhibits cold flow behav-
ior at all temperatures and does not work well as
a gasket material. In well confined applications
(such as valve packing), virgin PTFE can be used
successfully.
Because of its tendency to cold flow, PTFE for
gasket applications is typically filled with glass
fibers or ceramic particles to increase its dimen-
sional stability. Glass and ceramic filled PTFE
will absorb EO. EO polymerizes within the
PTFE-filler matrix and the resulting EO polymer
causes swelling and failure of the gasket. Glass
and ceramic filled PTFE gaskets are not durable
in EO service.
Spiral wound stainless steel gaskets filled with
virgin PTFE have been successfully used to seal
raised face flanges and valve bonnets in EO ser-
vice. However, there have also been quite a few
incidents where EO permeated into the PTFE
filler, polymerized, and caused deformation or
unwinding of the gasket. When spiral wound
gaskets are used in EO service, they should have
inner and outer retaining rings to prevent
unwinding of the gasket in case EO polymer
forms within the windings.
High purity (98%), flexible compressed
graphite is the most widely used gasket and pack-
ing material in EO service. This material has no
fillers or binders and is compatible with EO.
High purity, flexible compressed graphite is
available in flat sheet form as well as crinkled
tape for valve packing. The sheet form of flexi-
ble graphite is somewhat fragile, so for gasket
applications, the sheet is typically used as a filler
for stainless steel spiral wound gaskets. When
spiral wound gaskets are used in EO service, they
should have inner and outer retaining rings.
In EO service applications where spiral wound
gaskets cannot be used, laminated flexible com-
pressed graphite gaskets can be used. Several
manufacturers produce gaskets from two layers of
Design of Facilities
6- 2
Figure 6.1 Degradation of compressed
asbestos valve bonnet gaskets by EO
Figure 6.3 Deformation of a spiral wound
stainless steel-PTFE gasket due to EO perme-
ation and polymerization
Figure 6.4 Spiral wound stainless steel
flexible compressed graphite gasket with
inner and outer retaining rings
Figure 6.2 PTFE gasket failures in EO
service due to cold flow
flexible compressed graphite laminated to a
0.004" tang (perforated) stainless steel sheet.
Since the graphite is laminated to tang stainless
steel sheet, there are no adhesives used in the
lamination process. If a laminated gasket is
used, it is important to specify a tang stainless
steel sheet rather than flat stainless steel sheet.
Tests have shown that EO will attack the adhe-
sives that are used to bond flexible graphite to
flat stainless steel sheet.
Elastomers which are most commonly used to
make O-rings will often degrade in EO service.
Experience within the EO industry has shown
that there are a limited number of perfluoro
elastomers and EPDM elastomers that will hold
up well in EO service. Note that many of the
Kalrez, Chemraz, and EPDM formulations will
not hold up in EO service.
Following is a list of materials that have been
tested for compatibility with EO and have been
successfully used in EO service in industrial
applications.
O-Rings Chemraz
1
505
Kalrez
2
2035
Parker EPDM-740-75
Parker EPDM-962-90
Parker E-515-8-EPM
Gaskets Spiral wound stainless steel
with a high purity flexible com-
pressed graphite filler and inner
and outer retaining rings
(Polycarbon Sigraflex
3
B Grade or
UCAR Grafoil
4
GTB filler)
Laminated high purity flexible
compressed graphite on 0.004"
tang stainless steel sheet
(Polycarbon Sigraflex
3
BTCSS or
UCAR Grafoil
4
GHE)
Packing Corrugated flexible compressed
graphite ribbon (Polycarbon
Sigraflex
3
Corrugated B Tape or
UCAR Grafoil
4
GTZ)
Virgin PTFE rings or chevrons
1. Registered U.S. Trademark of Green Tweed and Company
2. Registered U.S. Trademark of E.I. DuPont De Nemours and Company
3. Registered U.S. Trademark of SGL Technic Inc., Polycarbon Division
4. Registered U.S. Trademark of UCAR Carbon Company Inc.
Durability of non-metallic materials in EO ser-
vice varies with the material used and with the
process conditions. The user should have an
inspection program to determine the durabil-
ity and required change-out frequency for the
materials selected for a given application.
Insulation
Insulation provides a degree of protection for
metal walls of vessels, piping and other
equipment against being heated to the initia-
tion temperature for EO decomposition by
external flames.
In selecting insulating materials for EO service,
the user should consider the following:
Porous insulating materials such as magne-
sium and calcium silicate, mineral wool,
and asbestos absorb water from the envi-
ronment. This can promote external
corrosion under insulation.
6- 3
Figure 6.5 Laminated gasket made of
Polycarbon Sigraflex BTCSS flexible
compressed graphite
Figure 6.6 Laminated gasket made of
UCAR Grafoil GH E flexible compressed
graphite
Porous insulating materials promote exother-
mic reactions such as that of EO with
absorbed water [5].
Aluminum sheathing on insulation has a rel-
atively low melting point. Stainless steel
sheeting/banding has superior durability in
the event of a fire.
The use of closed cell materials such as cellular
glass reduces the potential for water absorption
and for exothermic reactions in the event of an
EO leak under insulation. EO leaks under porous
insulation resulting in hot spots and internal
ignition have been implicated in major industrial
incidents. Two such incidents are discussed in
section 5.7.
As mentioned in the Metallic Materials sec-
tion, use of appropriate coatings on carbon steel
equipment that is to be insulated provides a
degree of protection against corrosion under
insulation. This is of special concern when the
operating temperature of the equipment is below
200F. This temperature range is too low to evap-
orate water that penetrates under the insulation.
6.4 Unloading Facilities
A number of incidents described in section 5.2
resulted from contamination of EO railcars.
Because of the seriousness of potential conse-
quences, the user must assure that shipping
containers are not contaminated from the
process. A key to prevention of contamination is
to provide a system totally dedicated to EO.
Facilities should not be designed for direct feed
from an EO railcar into a chemical process.
There should be intermediate storage down-
stream of the offloading facility, and systems to
prevent backflow from the process into EO
storage.
Design of Facilities
6- 4
To Process
To Scrubber
Tank
Car
Process And
Circulation Pump
With Low Flow, Deadhead
And Overheating Protection
(A) (B)
PI RV
PR 3
Relief
Valves
PR 1
PI
PR 2
LI
Ethylene Oxide
Storage Tank
WP
FI
Internal
Cooler
Nitrogen
Nitrogen
(G) (H)
RO
Lock or carseal open
Figure 6.8 Representative layout of Ethylene Oxide unloading facilities - Pressurized transfer
UNLOADINGWITHINERT GAS
1. Open liquid valves A, G
2. Open vapor valve B and apply nitrogen pressure
3. Open valve H as pressure builds up
NOTE: This diagram is for illustration purposes only.
Specific system design for individual applications must be
done only with consultation from professional engineer-
ing services or other qualified experts.
NOMENCLATURE
RO Restrictive orifice
TI Temperature indicating device
PI Pressure indicating device
PR 1 Pressure regulator - 35 psig setting min.
PR 2 Pressure regulator - 35 psig setting min.
PR 3 Pressure regulator - 60 psig setting max.
RV Safety valve set at 70 psig relieve
LI Level indicating device
WP Wash point valve
FI Flow indicator
Acceptable means of transfer from a railcar into
the storage facility are pressurization with an
inert gas and pumping. Typical layouts for a pres-
sure transfer facility and a pump transfer facility
are shown in Figures 6.7, 6.8 and 6.9. If pressur-
ization is used to unload railcars, a safe means of
venting off excess pressure is recommended.
Shipping empty railcars at unloading pressure
can result in releases from the safety relief valve
in transit. Pressurized transfer by heating is not
recommended.
Facilities for railcar loading and unloading
should be equipped with a water deluge system
that can be activated manually or by com-
bustible gas detectors or high temperature
sensors. An elevated rack for access to the rail-
car dome is preferred. Protection against
inadvertent movement of the railcar while the
loading/unloading hoses are connected is
required by DOT regulation.
6-5
Figure 6.9 Representative layout of Ethylene Oxide unloading facilities - Pump transfer
To Process
Lock or carseal open
To Scrubber
Tank
Car
Process And
Circulation Pump
With Low Flow, Deadhead
And Overheating Protection
(A) (B)
Relief
Valves
PR 1
PI
PR 2
LI
Ethylene Oxide
Storage Tank
WP FI
Internal
Cooler
Nitrogen
(G) (H)
(C)
FI
(D) (E)
Transfer Pump
With Low Flow, Deadhead
And Overheating Protection
(F)
RO
Figure 6.7 Ethylene Oxide unloading
facilities
UNLOADINGWITHTRANSFER PUMP
1. Open liquid valves A, D, E, G
2. Close liquid valve C
3. Open vapor valves B, F
NOTE: This diagram is for illustration purposes only. Specific
system design for individual applications must be done only
with consultation from professional engineering services or
other qualified experts.
NOMENCLATURE
RO Restrictive orifice
TI Temperature indicating device
PI Pressure indicating device
PR 1 Pressure regulator - 35 psig setting min.
PR 2 Pressure regulator - 35 psig setting min.
LI Level indicating device
WP Wash point valve
FI Flow indicator
6.5 Ethylene Oxide Storage
Design Considerations
Design considerations for storage vessels in EO
service should include:
Compliance with the current ASME Code
for Unfired Pressure Vessels for the mini-
mum design working pressure consistent
with process requirements, including consid-
eration of the blanket inert gas pressure
needed to maintain a non-decomposable
vapor space (see next page under Inerting
of Storage).
Adequate capacity to accept the entire con-
tents of the shipment container.
EO storage tanks should be located within a
diked area, or one otherwise designed to
contain a tank leak and to prevent other
product spills from entering the EO storage
area. The area should be adequately supplied
with fire water deluges and/or fixed fire
water monitors.
Because of its hazardous nature, the user of EO
should design storage facilities to minimize the
working inventory of EO.
Railcars should not be used for extended storage.
They cannot be monitored for temperature or
pressure increases as effectively as permanent
storage tanks. They also offer no means of heat
removal in the event of EO polymerization or
reaction with a contaminant.
Instrumentation
EO storage instrumentation must provide the
following:
Accurate level measurement.
Assurance that the storage vessel is inerted
at an adequate pressure to stay out of the
explosive region.
Reliable indication of heat release from a
contamination reaction.
Consider the following when designing instru-
ment systems for EO storage:
Installation of multiple, independent tem-
perature measurements, and alarming on
high temperatures.
Installation of multiple, independent level
measurements, or an independent high level
alarm.
Monitoring and alarming on rate of rise of
storage temperature. Changes in the rate
indicate intensification of a contamination
reaction and dictate when emergency
response plans should be activated.
Alarming on low pressure (low pressures
indicate loss of inerting gas).
Gauge glasses have potential for fitting leaks and
plugging from polymer formation. Using stain-
less steel instrument lines for EO service reduces
the likelihood of polymer formation and plug-
ging. The use of remote diaphragm sealed
differential pressure transmitters, bubbler dip
tubes, ultrasonic, radar and nuclear level indica-
tors can reduce the potential for erroneous level
indication caused by polymer formation. The
user should avoid use of mercury-containing
instrument systems (e.g., manometers), as mer-
cury is reactive with EO.
Inerting of Storage
Section 2.3 discusses the potential for pure EO
vapor to decompose explosively in the presence
of a suitable ignition source. EO vapor spaces
can be rendered non-decomposable by diluting
with the appropriate proportion of an inert gas.
In practice, vessels are inerted with nitrogen,
and are maintained in the non-decomposable
region by controlling pressure.
Figure 6.10 shows minimum storage pressures
required to ensure that EO vapor spaces are
non-decomposable, as a function of liquid stor-
age temperature. The figure assumes use of
nitrogen as the inerting gas. No margin of
safety has been incorporated into this
graph [6].
Inerting systems are themselves potential
sources of contamination and EO users should
carefully evaluate this potential. Systems in
place to prevent inert gas contamination
include:
Design of Facilities
6- 6
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6-7
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
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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
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.
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1
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0
.
0
1
1
0
.
0
1
2
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.
0
1
3
F
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E

8
:

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t
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e

O
x
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d
e

V
a
p
o
r

V
i
s
c
o
s
i
t
y
T
e
m
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r
a
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e
,



F

0
1
2
0
2
0
0
2
4
0
1
6
0
4
0
8
0
A-9
F
I
G
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R
E

8
:
B T U / F t * H r * F
T
e
m
p
e
r
a
t
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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
0
.
0
0
9
0
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.
0
1
1
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0
1
2
0
.
0
1
3
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F
I
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9
:

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t
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e

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a
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h
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m
a
l

C
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n
d
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c
t
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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
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4
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1
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t
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y
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n
e

O
x
i
d
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i
n

W
a
t
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r
,

w
t
%
F
r
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z
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g

P
o
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t
s

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W
a
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p
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7
0


F

F
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0
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/ C
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R a t i o
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,



F

1
.
2
5
1
.
2
4
1
.
2
3
1
.
2
2
1
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2
6
1
.
2
7
1
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8
1
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2
9
1
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3
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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
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p
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r

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s
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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
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9
0
.
0
0
1
1
0
.
0
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1
3
0
.
0
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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
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p
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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
[1] C. Hirose, Bull. Chem. Soc. Jpn, 47,
No. 6 (1974), pp. 1311-1318.
[2] A. Wurtz, Justus Liebigs Ann. Chem.,
110 (1859), pp. 125-128.
[3] Societe Francaise de Catalyse
Generalisee. FR 729 952, 1931; 739
562, 1931 (T. E. Lefort).
[4] O. Maas and E. H. Boomer, J. Am.
Chem. Soc., 44 (1922), p. 1709.
[5] D. N. Glew and N. S. Rath, J. Chem.
Phys., 44 (1965), p. 1711.
[6] L. G. Hess and V. V. Tilton, Ind. Eng.
Chem., 42 (1950), no. 6, pp. 1251-
1258.
[7] J. D. Olson, J. Chem. Eng. Data, 22
(1977), p. 326.
[8] G. O. Curme: Gycols, (New York,
Reinhold Publ. Co., 1952), pp. 74-113.
[9] 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,
Wiley, New York, 1994.
[10] Rebsdat, Siegfried, and Mayer, Dieter
Ethylene Oxide. Ullmanns
Encyclopedia of Industrial Chemistry,
NY (1987).
[11] A. Weissberger, Heterocyclic
Compounds, ed. A Rosowski, vol. 19,
Wiley-Interscience, New York 1964,
pp. 1-523.
[12] I. Parker, Chem. Rev. 59 (1959),
pp. 737-797.
[13] N. Schonfeld, Surface Active Ethylene
Oxide Adducts, Pergaman, NY (1969).
[14] J. Gorzinski Smith, Synthesis, 8 (1984),
pp. 629-656.
[15] B. Pesetsky, Chem. Eng. Prog. Loss.
Prev., 13 (1980), pp. 132-141.
[16] R. R. Baldwin, A. Keen, R. W. Walker,
J. Chem. Soc. Faraday Trans. 1,80
(1984), no. 2, pp. 435-456.
[17] Britton, Laurence G; Thermal stability
and deflagration of ethylene oxide
Plant/Operations Progress, vol. 9,
pp. 275-86, April 1990.
[18] D. R. Stull, AICHE Monograph Series,
73 (1977), no. 10, pp. 67-68.
[19] T. H. Baize, Ind. Eng. Chem., 53
(1961), p. 903.
[20] D. Conrad, Bundesgesundheitsblatt,
9 (1963), pp. 139-141.
[21] W. H. Perkin, J. Chem. Soc., 63 (1893),
p. 488.
[22] Y. Hashigushi, Tokyo Kogyo Shikensho
Hokoku, 60 (1965), no. 3, pp. 85-91.
[23] J. Osugi, M. Okusima, and
M. Hamanoue, Koatsu Gasu, 8 (1971),
no. 4, pp. 201-206.
[24] S. N. Bajpai, Chem. Eng. Prog. Loss
Prev. Technical Manual, 13 (1980),
pp. 119-122.
[25] J. H. Burgoyne and K. E. Bett,
Inst. Chem. Eng. Symp. Ser., 25 (1968),
pp. 1-7.
[26] J. H. Burgoyne and K. E. Bett and
R. Muir, Symposium on Chem. Proc.
Hazards (Inst. Chem. Eng.), ed J. M.
Piric, (1960), pp. 30-36.
[27] A. Fiumara and N. Mazzei, Chim. Ind.
(Milan), 65 (1983), no. 11,
pp. 683-687.
[28] E. O. Haenni, N. A. Affens, H. G.
Lento, A. H. Yeomans and R. A.
Fulton, Ind. Eng. Chem., 51 (1959),
No. 5, pp. 685-688.
Appendix B: References
B- 1
[29] L. Cider and L. Vamling, Ind. Eng.
Chem. Prod. Res. Dev., 25 (1986),
No. 3, pp. 424-430.
[30] D. N. Kirk, Chem. Ind., (London,
1973), No. 3, pp. 109-116.
[31] F. T. Bodurtha, Industrial Explosion
Prevention and Protection, McGraw-
Hill, 1980.
[32] F. G. Eichel, Electrostatics, Chemical
Engineering, March 13, 1967.
[33] Plant Operations Progress, Vol. 7,
No. 1. January 1988.
[34] D. D. Wagman, et al, The NBS Tables
of Chemical Thermodynamic
Properties, J. Phys. Chem Ref. Data,
Vol 11, Suppl.3, 1982.
[35] CRC Handbook of Themophysical and
Thermochemical Properties, CRC Press
1994.
[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,
Bulletin L-7160, Flammability Of
Diluted Ethylene Oxide at Low
Pressures,1992.
[39] V. Schroder and D Conrad, Chem. Ing.
Tech., 65(1993), no3. pp. 333-335.
[40] Y. Hashiguchi, et al., Kogyo Kayaku
Kyokaishi, 28(1967), No 2, pp. 128-31.
[41] M. Chaigneau, Ann. Pharm. Franc., 43
(1985), pp. 193-194.
[42] G. A. Viera, L.L. Simpson, and B. C.
Ream, Lessons Learned from the
Ethylene Oxide Explosion at Seadrift
Texas, Chemical Engineering Progress,
August 1993.
[43] Shell Chemical Company Internal
Communication.
[44] Product Catalog from Polysciences,
Inc., Polymer/Monomer Catalog 1996-
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.
Brit. J. Industrial Med., 50, 971-997,
1993.
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
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Chemicals. Van Nostrand Reinhold,
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Appendix B: References
B-5