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ethyleneoxide

third edition
Legal Notice
The Ethylene Oxide Product Stewardship Neither the American Chemistry Council, nor the
Guidance Manual was prepared by the American individual member companies of the Ethylene
Chemistry Councils Ethylene Oxide/Ethylene Oxide/Ethylene Glycols Panel, nor any of their
Glycols Panel (Panel). It is intended to provide respective directors, officers, employees,
general information to persons who may handle subcontractors, consultants, or other assigns,
or store ethylene oxide. It is not intended to makes any warranty or representation, either
serve as a substitute for in-depth training or express or implied, with respect to the accuracy
specific handling or storage requirements, nor is or completeness of the information contained
it designed or intended to define or create legal in this manual; nor do the American Chemistry
rights or obligations. It is not intended to be a Council or any member companies assume any
how-to manual, nor is it a prescriptive guide. All liability or responsibility for any use or misuse,
persons involved in handling and storing ethylene or the results of such use or misuse, of any
oxide have an independent obligation to ascertain information, procedure, conclusion, opinion,
that their actions are in compliance with current product, or process disclosed in this manual.
federal, state and local laws and regulations and NO WARRANTIES ARE GIVEN; ALL IMPLIED
should consult with legal counsel concerning WARRANTIES OF MERCHANTABILITY OR FITNESS
such matters. The manual is necessarily general FOR A PARTICULAR PURPOSE ARE EXPRESSLY
in nature and individual companies may vary their EXCLUDED.
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and economic and technological feasibility. Any to the following limitations: (1) the work must be
mention of specific products in this manual is reproduced in its entirety, without alterations; and
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as a recommendation or endorsement of such
products. For more information on material presented in this
manual, please contact your supplier.
Copyright May 2007
ethyleneoxide
third edition
To the Reader
Manual Preparation Tom Grumbles Sasol North America

As members and affiliated companies of the Susan Jackson BASF Corporation


American Chemistry Council, we support efforts to Robert Lenahan Bayer MaterialScience LLC
improve the industrys responsible management
Denis Reeser The Dow Chemical Company
of chemicals. To assist in this effort, the American
Chemistry Councils Ethylene Oxide/Ethylene John Stewart BASF Corporation
Glycols Panel supported the creation and Don Szczepanski Huntsman Petrochemical
publication of this manual. The Panel is comprised Corporation
of the following companies:
David Townsend Celanese Chemicals Ltd.
Balchem Corporation/ARC Specialty Products
Randy Viscomi Balchem Corporation/ARC
BASF Corporation Specialty Products
Bayer Material Science LLC Keith Vogel Lyondell Chemical Company
Celanese Ltd. Mike Wagner Old World Industries
Champion Technologies John Wincek Croda, Inc.
Croda, Inc. Gerald Wise Shell Chemical LP
The Dow Chemical Company
Acknowledgements
Eastman Chemical Company
Many others contributed to the development and
Honeywell
editing of this manual, all of whom cannot be listed
Shell Chemical LP here; however, the manual work group would like to
The development of this manual was led by the thank the following individuals for their significant
Panels Ethylene Oxide Safety Task Group (EOSTG), contributions to this publication:
a group comprised of producers and users of Ralph Gingell Shell Chemical LP
ethylene oxide. The EOSTG functions to generate,
William Gulledge American Chemistry Council
collect, evaluate and share information to support
product stewardship with regard to ethylene oxide. Karl Loos Shell Chemical LP
The EOSTG formed a manual work group, chaired David McCready The Dow Chemical Company
by Keith Vogel of Lyondell Chemical Company,
Kristy Morrison EO STG Manager, American
to lead the development of this document. The
Chemistry Council
following work group members provided significant
contributions: Karyn Schmidt Assistant General Counsel,
American Chemistry Council

ii Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007


Table of Contents

Table of Contents
1.0 Introduction . . . . . . . . . . . . . . . . . . . . 1 6.0 Design of Facilities . . . . . . . . . . . 39
1.1 Purpose and Use of Manual . . . . 1 6.1 Introduction . . . . . . . . . . . . . . . . 39

2.0 Properties of Ethylene Oxide . . 2 6.2 Plant Layout and Siting . . . . . . 39

2.1 Introduction . . . . . . . . . . . . . . . . . 2 6.3 Materials of Construction . . . 40

2.2 Physical Properties . . . . . . . . . . . 3 6.4 Unloading Facilities


Bulk Receipt of EO . . . . . . . . . 46
2.3 Reactive and Combustive
Properties . . . . . . . . . . . . . . . . . . . 5 6.5 EO Storage . . . . . . . . . . . . . . . . 49

2.4 Commercial Chemistry . . . . . . 14 6.6 Reaction Systems . . . . . . . . . . 54

2.5 Uses of Ethylene Oxide . . . . . . 15 6.7 Piping and Pumps . . . . . . . . . . . 57


6.8 Handling of Vents and
3.0 Health Effects of Effluent . . . . . . . . . . . . . . . . . . . 63
Ethylene Oxide . . . . . . . . . . . . . . . . 16
6.9 Miscellaneous . . . . . . . . . . . . . 66
3.1 Introduction . . . . . . . . . . . . . . . . 16
3.2 Acute Inhalation Exposure . . . . 16 7.0 Personnel Exposure . . . . . . . . . . 68
3.3 Skin and Eye Contact . . . . . . . . 16 7.1 Introduction . . . . . . . . . . . . . . . 68

3.4 Chronic Exposure Hazards . . . 16 7.2 OSHA Standard for Ethylene


Oxide . . . . . . . . . . . . . . . . . . . . . 68
4.0 Environmental Effects of 7.3 Other Exposure Standards/
Ethylene Oxide . . . . . . . . . . . . . . . . 18 Recommendations for
4.1 Introduction . . . . . . . . . . . . . . . . 18 Ethylene Oxide . . . . . . . . . . . . . 68
4.2 Properties in the Environment 18 7.4 Measuring Exposure . . . . . . . . . 70
4.3 Ecotoxicological Effects . . . . . . 21 7.5 Personal Protective
4.4 Environmental Evaluation of Equipment . . . . . . . . . . . . . . . . . 70
Ethylene Oxide Spills . . . . . . . . 21 8.0 Equipment Preparation
4.5 Fugitive Emissions . . . . . . . . . . 22 and Maintenance . . . . . . . . . . . . . 82
5.0 Hazards of Ethylene Oxide . . . . 23 8.1 Introduction . . . . . . . . . . . . . . . . 82

5.1 Introduction . . . . . . . . . . . . . . . . 23 8.2 Preparation for Inspection or


Maintenance . . . . . . . . . . . . . . . 82
5.2 Contamination Incidents . . . . . 23
8.3 Preparation of Internal
5.3 Formation of Ethylene Oxide Surfaces . . . . . . . . . . . . . . . . . 83
Vapor Clouds . . . . . . . . . . . . . . . 27
8.4 Leak Repair Clamps . . . . . . . . 83
5.4 Ethylene Oxide Decomposition
Incidents . . . . . . . . . . . . . . . . . . 27 8.5 Preventive Maintenance . . . . . 84

5.5 Ethylene Oxide Transportation 8.6 Equipment Commissioning . . 84


Incidents . . . . . . . . . . . . . . . . . . . 35 9.0 Transportation and
5.6 Runaway Ethylene Oxide Unloading Operations . . . . . . . . . 85
Polymerization Incidents . . . . . 36 9.1 Introduction . . . . . . . . . . . . . . . 85
5.7 Runaway Reactions in 9.2 Emergency Response
Ethoxylation Units . . . . . . . . . . . 36 Telephone Numbers . . . . . . . . . 85
5.8 Incidents in Ethylene Oxide 9.3 Ethylene Oxide Classification . 85
Abatement Devices . . . . . . . . . . 37

Copyright May 2007 Ethylene Oxide Product Stewardship Guidance Manual iii
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9.4 Railcars . . . . . . . . . . . . . . . . . . . . 85 11.0 Selected Regulations . . . . . . . 105


9.5 IM Portable Tanks 11.1 Introduction . . . . . . . . . . . . . . . 105
(Intermodal/Iso-Containers) . 94
11.2 Regulations Numerical
9.6 Non-Bulk Packaging for with Subject Listed . . . . . . . . . 105
High Purity Ethylene Oxide . . 94
Appendix A
9.7 Ethylene Oxide Shipping
Figures and Tables . . . . . . . . . . 118
Data . . . . . . . . . . . . . . . . . . . . . 98
9.8 Shipments of Ethylene Oxide Appendix B
between the U.S. and Laboratory Compatibility
Canada . . . . . . . . . . . . . . . . . . . 98 Testing of Elastomers with
Ethylene Oxide . . . . . . . . . . . . . . . 137
10.0 Emergency Response . . . . . . . 100
Appendix C
10.1 Introduction . . . . . . . . . . . . . . 100
Railcar Repressurization . . . . . 141
10.2 Potential Hazards . . . . . . . . . . 100
Appendix D
10.3 Fire Response . . . . . . . . . . . . . 101
References . . . . . . . . . . . . . . . . . . . 145
10.4 Spill Response . . . . . . . . . . . . . 102
Appendix E
10.5 Emergency Response to
Glossary of Selected
Temperature Rise . . . . . . . . . . 102
Terms, Abbreviations and
10.6 Emergency Response Plan Organizations . . . . . . . . . . . . . . . . 151
to Temperature Rise . . . . . . . . 103
10.7 Use of Water in
Emergencies . . . . . . . . . . . . . . 104

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Figures Figure 5.9 Remnants of Railcar


(after EO explosion caused
Figure 2.1 The Ethylene Oxide
by contamination with
Molecule . . . . . . . . . . . . . . . . . . 2
ammonia) . . . . . . . . . . . . . . . . . 26
Figure 2.2 Flammable Region of
Figure 5.10 High Speed Centrifugal
Ethylene Oxide/Nitrogen/Air
Pump Launched by
Mixtures . . . . . . . . . . . . . . . . . . . 7
Decomposition of 0.6 Pounds
Figure 2.3 Flammable Region of of Ethylene Oxide . . . . . . . . . 29
Ethylene Oxide/Carbon
Figure 5.11 Motor Landed on Operating
Dioxide/Air Mixtures . . . . . . . . . 7
Ethylene Oxide Pump
Figure 2.4 Effects of Pressure on Discharge Line . . . . . . . . . . . . 29
Flammable Region of
Figure 5.12 Ethylene Oxide Distillation
Ethylene Oxide/Nitrogen/Air
Column Reboiler after
Mixtures . . . . . . . . . . . . . . . . . . 8
Explosion . . . . . . . . . . . . . . . . 30
Figure 2.5 Ethylene Oxide Polymer
Figure 5.13 Aerial View of Ethylene
Instantaneous Drop-Out
Oxide Plant after Explosion . . 31
Temperatures . . . . . . . . . . . . 13
Figure 5.14 Remnants of Base of
Figure 2.6 Ethylene Oxide Polymer
Ethylene Oxide Distillation
Drop-Out Temperatures
Column after Explosion . . . . . 31
after 4 Days . . . . . . . . . . . . . . 14
Figure 5.15 Piece of Ethylene Oxide
Figure 4.1 Neutral EO/Water/Glycol
Distillation Column Wall
Kinetics - Isothermal Case,
Turned Inside Out by
Initially EO/Water mixture . . 19
Explosion . . . . . . . . . . . . . . . . . 32
Figure 4.2 Neutral EO/Water/Glycol
Figure 5.16 Aerial View of EO Unit
Kinetics - Adiabatic Case,
After Explosion . . . . . . . . . . . . 33
Initially EO/Water . . . . . . . . . . 19
Figure 5.17 EO Plant Burning
Figure 5.1 Older View of Plant Before
after Explosion . . . . . . . . . . . . 33
Explosion Showing EO Tanks
in Foreground . . . . . . . . . . . . . . . 23 Figure 5.18 EO Purification After
Explosion Two Towers
Figure 5.2 Blast Center after
are Missing . . . . . . . . . . . . . . 34
Explosion EO Vessels
No Longer Visible . . . . . . . . . . 23 Figure 5.19 Ethylene Oxide Re-distillation
Tower Explosion . . . . . . . . . . 34
Figure 5.3 Aerial View of the Plant
Showing Overall Damage . . . 24 Figure 5.20 Resulting Damage to the
Plant . . . . . . . . . . . . . . . . . . . . 34
Figure 5.4 EO Tank Blown Into Process
Structure 400 Feet Away . . . 24 Figure 5.21 Filter Case after Runaway
Polymerization . . . . . . . . . . . . 36
Figure 5.5 Plant Laboratory After
EO Vapor Cloud Explosion, Figure 5.22 Filter Case after Runaway
300 Feet Away from Polymerization . . . . . . . . . . . . 36
Explosion Center . . . . . . . . . . 25 Figure 5.23 Filter Case after Runaway
Figure 5.6 Remnants of Railcar . . . . . . . 25 Polymerization . . . . . . . . . . . . 36
Figure 5.7 Remnants of Railcar . . . . . . . 25 Figure 5.24 Diagram of Sterilizer
Explosion . . . . . . . . . . . . . . . . . 37
Figure 5.8 Damage to Other Railcars
from Ethylene Oxide Railcar Figure 5.25 Sterilizer Explosion
Explosion . . . . . . . . . . . . . . . . . 25 Damage . . . . . . . . . . . . . . . . . 38

Copyright May 2007 Ethylene Oxide Product Stewardship Guidance Manual v


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Figure 5.26 Sterilization Chamber Figure 6.11 Example of Severely


Damage . . . . . . . . . . . . . . . . . 38 Degraded O-ring in High
Figure 5.27 Damage to the building Temperature EO-water
wall from impact of sterilizer Service (Chemraz 505) . . . 44
door . . . . . . . . . . . . . . . . . . . . 38 Figure 6.12 Example of Flange Seal
Figure 6.1 Degradation of Compressed Band with Leak Detection
Asbestos Valve Bonnet Drip Tube . . . . . . . . . . . . . . . . 45
Gaskets by Ethylene Oxide . . 41 Figure 6.13 EO Unloading Facilities . . . . 46
Figure 6.2 PTFE Gasket Failures in EO Figure 6.14 Representative layout of
Service Due to Cold Flow . . . 41 Ethylene Oxide unloading
Figure 6.3 Glass Filled PTFE Gasket facilities Pressurized
Failure Due to EO transfer . . . . . . . . . . . . . . . . . . 47
Polymerization in Figure 6.15 Representative layout of
PTFE-Glass Matrix . . . . . . . . . 42 Ethylene Oxide unloading
Figure 6.4a Deformation of a Spiral Wound facilities Pump transfer . . 48
Stainless Steel-PTFE Gasket Figure 6.16 Total pressure required to
Due to EO Permeation and inert vapor above Ethylene
Polymerization . . . . . . . . . . . . 42 Oxide with nitrogen diluent . 51
Figure 6.4b Deformation of a Spiral Figure 6.17 EO Decomposable Limits
Wound Stainless Steel-PTFE versus Molar Nitrogen
Gasket . . . . . . . . . . . . . . . . . . . 42 Concentration . . . . . . . . . . . . . 56
Figure 6.5 Spiral Wound Gasket with Figure 6.18 Decomposition Limit of
Stainless Steel Windings, Mole % EO versus Total
Flexible Compressed Graphite System Pressure . . . . . . . . . . 57
Filler, and Inner and Outer Figure 6.19 Ethylene Oxide Vent
Retaining Rings . . . . . . . . . . . 43 Scrubber System . . . . . . . . . 63
Figure 6.6 Gasket Test Showing Failure Figure 6.20 Schematic of Typical
of Compressed Graphite Flaring System . . . . . . . . . . . . 65
Gasket, Laminated on Flat
Stainless Steel Sheet with Figure 6.21 EO Sampling System . . . . . . . 67
an Adhesive . . . . . . . . . . . . . 43 Figure 7.1 OSHA Warning for EO
Figure 6.7 Laminated Gasket Made of Regulated Areas . . . . . . . . . 69
Polycarbon Sigraflex Figure 7.2 Chemical Burn Resulting
BTCSS Flexible Compressed from Low Concentration
Graphite Laminated on of EO in Water . . . . . . . . . . . . . 70
Stainless Steel Tang Sheet . 43 Figure 9.1 DOT 105-J railcar for
Figure 6.8 Laminated Gasket Made of transporting Ethylene Oxide 86
UCAR Grafoil GH E Flexible Figure 9.2 Dome Arrangement of a
Compressed Graphite DOT 105-J Railcar for
Laminated on Stainless Ethylene Oxide Service . . . . . 87
Steel Tang Sheet . . . . . . . . . 43
Figure 9.3 DOT StopTank Car
Figure 6.9 Butyl Rubber O-Ring Before Connected Sign . . . . . . . . 88
and After Exposure to EO
for 30 days . . . . . . . . . . . . . . 44 Figure 9.4 Canister Mask with Ethylene
Oxide-Specific Canister . . . 90
Figure 6.10 Example of Degraded
O-ring Attacked by EO . . . . 44

vi Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007


Table of Contents

Figure 9.5 Positive Pressure Hoseline Figure 16 Flammability Data on EO-Air


Type Respirator . . . . . . . . . . 90 Mixtures at Subatmospheric
Figure 9.6 Commonly Used Non-bulk Pressures . . . . . . . . . . . . . . . . 128
Containers . . . . . . . . . . . . . . . . 95 Figure 17 Vapor/Liquid Equilibria of
Figure 9.7 Typical Drum Connections . 96 Ethylene Oxide/Water
Systems . . . . . . . . . . . . . . . . . 129
Figure 10.1 Ethylene Oxide / Water
(Neutral) Reaction Figure 18 Density vs. Composition of
Temperature Profile . . . . . . . 103 Ethylene Oxide/Water
Systems . . . . . . . . . . . . . . . . . 130
Figure 1 Ethylene Oxide Liquid
Density . . . . . . . . . . . . . . . . . . 118 Figure 19 Boiling points of aqueous
EO concentrations . . . . . . . . 131
Figure 2 Ethylene Oxide Vapor
Pressure . . . . . . . . . . . . . . . . . 118 Figure 20 Decomposition Data . . . . . . 132

Figure 3 Ethylene Oxide Liquid Figure 21 Vapor Compressibility vs.


Heat Capacity . . . . . . . . . . . . 119 Pressure as a Function of
Temperature . . . . . . . . . . . . . 133
Figure 4 Ethylene Oxide Liquid
Viscosity . . . . . . . . . . . . . . . . 119 Figure B1 Weight Change of O-rings
Exposed to EO at 27C . . . . 138
Figure 5 Ethylene Oxide Liquid
Thermal Conductivity . . . . . 120 Figure B2 Volume Change of O-rings
Exposed to EO at 27C . . . . 138
Figure 6 Ethylene Oxide Heat of
Vaporization . . . . . . . . . . . . . 120 Figure B3 Tensile Strength of O-rings
Exposed to EO at 27C . . . . 140
Figure 7 Ethylene Oxide Vapor
Heat Capacity . . . . . . . . . . . . 121 Figure B4 Maximum Deformation of
O-rings Exposed to EO
Figure 8 Ethylene Oxide Vapor at 27C . . . . . . . . . . . . . . . . . . 140
Viscosity . . . . . . . . . . . . . . . . 121
Figure C1 Unloaded Railcar
Figure 9 Ethylene Oxide Vapor Repressuring Nitrogen
Thermal Conductivity . . . . . 122 Less than 50 Gallon
Figure 10 Freezing Points Ethylene EO Heel . . . . . . . . . . . . . . . . . 142
Oxide/Water Mixtures . . . . . 122 Figure C2 Unloaded Railcar
Figure 11 Cp/Cv For Saturated Repressuring Vapor
Ethylene Oxide Vapor . . . . . 123 Balancing Less than
Figure 12 Ethylene Oxide Vapor 50 Gallon Heel . . . . . . . . . . . 144
Density . . . . . . . . . . . . . . . . . . 123
Figure 13 Ethylene Oxide Coefficient
of Cubic Expansion . . . . . . . 124
Figure 14 Raoults Law Deviation
Factors for Ethylene Oxide/
Water Mixtures . . . . . . . . . . . 126
Figure 15 Raoults Law Deviation
Factors for Ethylene Oxide/
Water Mixtures . . . . . . . . . . . 127

Copyright May 2007 Ethylene Oxide Product Stewardship Guidance Manual vii
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Tables Table 7.2 OSHA Minimum Standards


for Respiratory Protection for
Table 2.1 Physical Properties of
Airborne Ethylene Oxide . . . . 72
Ethylene Oxide . . . . . . . . . . . . . 3
Table 7.3 Ethylene Oxide Permeation
Table 2.2 Physical Properties of
Data for Clothing . . . . . . . . . . 73
Aqueous Ethylene Oxide
Solutions . . . . . . . . . . . . . . . . . . 5 Table 7.4 Ethylene Oxide Permeation
Data for Gloves . . . . . . . . . . . 79
Table 2.3 Heat of Reaction of Various
Ethylene Oxide Reactions Table 7.5 Ethylene Oxide Permeation
at 25C . . . . . . . . . . . . . . . . . . . . 6 Data for Boots . . . . . . . . . . . . . 81
Table 2.4 Physical Properties of Table 9.1 Illustration Pressuring
Ethylene Oxide Polymer . . . . 12 Unloaded Railcars with
Pure Nitrogen (Assuming
Table 2.5 Solubility* of Ethylene
50 Gallon Ethylene Oxide Liquid
Oxide Polymer in Various
Heel) . . . . . . . . . . . . . . . . . . . . . 93
Solvents . . . . . . . . . . . . . . . . . . 13
Table 9.2 Illustration Repressuring
Table 3.1 Carcinogenicity
Unloaded Railcars Vapor
Classifications of
Balancing (50 Gallon Ethylene
Ethylene Oxide . . . . . . . . . . . . 17
Oxide Liquid Heel) . . . . . . . . 94
Table 3.2 Findings of the NIOSH
Table 9.3 Temperature/Density/Vapor
Ethylene Oxide Studies . . . . 17
Pressure for Shipping
Table 4.1 Environmentally Relevant Ethylene Oxide . . . . . . . . . . . 98
Parameters of Ethylene
Table A1 Physical Property
Oxide . . . . . . . . . . . . . . . . . . . . 18
Equations . . . . . . . . . . . . . . . . 134
Table 4.2 Biological Degradation
Table A2 Conversion Factors . . . . . . . 134
Data for Ethylene Oxide . . . 20
Table A3 Henrys Law Constants
Table 4.3 Aquatic Toxicity Data for
(Atm/mole fraction) . . . . . . . 135
Ethylene Oxide* . . . . . . . . . . . 21
Table A4 Henrys Law Constants
Table 6.1 EO Pump Shutdown and
(MPa/mole fraction) . . . . . . . 135
Alarm Considerations . . . . . . 62
Table B1 O-Rings Selected for
Table 7.1 AEGL Values for Ethylene
Compatibility Testing . . . . . 137
Oxide [ppm (mg/m3)] . . . . . . 69

viii Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007
5.0 Hazards of Ethylene Oxide

5.0 Hazards of Ethylene Oxide


5.1 Introduction Contamination of Ethylene Oxide
EO has been involved in incidents in both EO with Aqueous Ammonia
production plants and EO consuming plants In a 1962 incident at an EO production and
[1] resulting in major plant damage as well as derivatives plant, an EO storage vessel containing
fatalities. EO has also been involved in significant 21 tons of EO was contaminated with aqueous
transportation incidents. ammonia due to backflow from an ethanolamines
One of the best ways for the EO user to understand unit. The EO and ammonia rapidly reacted in the
the hazards of EO is to become familiar with vessel; the overpressured vessel ruptured; and an
historical incidents. This Chapter reviews some EO vapor cloud explosion occurred. (Figures5.1,
incidents involving EO that are particularly 5.2, 5.3, 5.4, 5.5). The primary explosion threw an
instructive in understanding EO hazards. It is hoped adjacent EO storage vessel containing 13tons
that the lessons to be learned from incidents like of EO into another process structure 400feet
these will assist in future plant design as well as away. Numerous vessels in the area of the primary
in the development of procedures for operations, explosion ruptured during the vapor cloud
maintenance, training and emergency response. explosion or during the resulting fires at the site.

Figure 5.1 Older View of Plant Before


5.2 Contamination Incidents
Explosion Showing EO Tanks
EO is routinely reacted with other chemicals under in Foreground
controlled conditions to produce commercial
products. Because EO is reactive with so many
other chemicals and the resulting reactions are
highly exothermic, contamination is one of the most
significant hazards of working with EO.
Contamination of pure EO with waste materials or
other chemicals including water can lead to
uncontrolled reactions producing large amounts of
heat. Generation of heat from the reaction of EO
and contaminants or from the polymerization of EO
can overpressure and rupture the EO-containing
vessel. In a contamination incident, the EO-
containing vessel typically ruptures long before all
the EO has reacted. The sudden depressurization
Figure 5.2 Blast Center after Explosion
when the vessel ruptures results in the formation of
EO Vessels No Longer Visible
an EO vapor cloud.
EO contamination incidents can be described
as kindling chain events. A typical description
of such a chain of events is as follows: a small
contamination of an EO vessel leads to a reaction
of EO in the vessel, which leads to an overpressure
and rupture of the vessel, which leads to formation
of an EO vapor cloud, which subsequently
results in a vapor cloud explosion. In many of the
contamination incidents discussed below, as well as
many of the EO decomposition incidents, most of
the resulting damage was due to an EO vapor cloud
explosion.

Copyright May 2007 Ethylene Oxide Product Stewardship Guidance Manual 23


5.0 Hazards of Ethylene Oxide

Figure 5.3 Aerial View of the Plant Figure 5.4 EO Tank Blown Into Process
Showing Overall Damage Structure 400 Feet Away

Ignition of the EO vapor cloud caused extremely


heavy structural damage in a radius of 500 feet
from the blast center. Implosion damage occurred
in a radius of 700 1,000 feet from the blast
center. Buildings and equipment within a radius of
1,000 feet of the blast center suffered extensive
glass breakage and minor structural damage. The
explosion could be heard 35 miles away from the
plant and evidence of the shock wave from the
explosion was noted up to three miles away. The
explosion resulted in one fatality, three serious
injuries and 18 less serious injuries.
The EO producers investigation revealed that rail yard. (Figures 5.6, 5.7, 5.8). The EO producers
ammonia backflowed from the EO transfer line investigation revealed that a major contributing
into the EO storage vessel. The ammonia passed factor to this incident was slow addition of water
through several check valves and a positive to the railcar, which helped the EO and water
displacement pump (through its relief valve) before which have different densities resist mixing. The
entering the EO vessel [2,3]. EO and water collected in two layers in the railcar,
and the formation of these layers meant that
Railcar Explosion Due to Reaction there was a large area of interface between high
Between Residual Ethylene Oxide concentration EO and high concentration water.
and Cleaning Water This resulted in a much higher reaction rate than
In this incident, an EO railcar was sent to a would have occurred if the EO and water had been
contractor for cleaning prior to maintenance on well mixed. Contaminants in the brackish water
the railcar. Unknown to the cleaning contractor, may have also contributed to the high reaction
the railcar contained a heel of a few thousand rate. The subsequent reaction generated high
gallons of EO. The contractor pumped brackish temperature and pressure in the railcar, resulting
water into the car and left it in a rail yard in its rupture [4].
overnight. During the night the railcar exploded,
causing significant damage to other railcars in the

24 Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007


5.0 Hazards of Ethylene Oxide

Figure 5.5 Plant Laboratory After EO Vapor Figure 5.7 Remnants of Railcar
Cloud Explosion, 300 Feet Away
from Explosion Center

Figure 5.8 Damage to Other Railcars from


Ethylene Oxide Railcar Explosion
Figure 5.6 Remnants of Railcar

Ethylene Oxide Railcar Contamination plant thought the car contained anhydrous
with Bentonite Clay ammonia. They attempted to offload the EO into
an anhydrous ammonia vessel. The ammonia
A railcar was returned to an EO producers plant
vessel was at a significantly higher pressure than
after cleaning by a contractor. The contractor
the pressure on the EO railcar. During the attempt
had put bentonite clay (a drying agent) in the car
to offload the EO, a check valve leaked and
to reduce rust formation. The EO producer was
allowed a small amount of ammonia to backflow
unaware of the use of clay and did not remove it
into the EO railcar. When the workers at the plant
when the railcar was received at the plant. During
discovered that the car was delivered by mistake,
loading of the railcar with EO, a fire occurred in
the unloading operation was stopped and the
the railcar dome. Reaction between the bentonite
car containing the contaminated EO was sent to
clay and EO caused an internal ignition and release
its proper destination, 300 kilometers (180 miles)
of burning EO vapor through the railcars safety
away. The railcar exploded in the middle of the
relief valve. The fire was initially extinguished with
night on a rail siding at the edge of the plant.
water but it re-flashed. The fire was ultimately
The explosion destroyed an adjacent warehouse,
extinguished with dry chemical.
caused major damage over a 300 meter radius and
Contamination of Railcar with Ammonia broke windows up to 5 kilometers (3 miles) away.
(Figure5.9).
A European EO producer shipped an EO railcar
to a customer. The railcar was delivered to the
wrong plant and the workers at the receiving
Copyright May 2007 Ethylene Oxide Product Stewardship Guidance Manual 25
5.0 Hazards of Ethylene Oxide

Explosion of Railcar Containing EO and water [5]. For more information on EO-water
Ethylene Oxide Washwater mixtures, see Chapter 2.

In an incident occurring in December 1973, an EO Contamination of Ethylene Oxide Plant


producer in the U.S. washed an EO ship loading Nitrogen Source with EO
line and an EO storage sphere with river water and
then stored the EO contaminated water in a 22,500 This incident involves a European EO plant, in
gallon railcar. The railcar contained 8000 gallons of which vessels were padded with 5-bar nitrogen
EO at 43F (6C) and 5200 gallons of wash water at from a central line. The equipment for feeding
63F (17C). The railcar was padded with nitrogen at nitrogen consisted of a check valve and a
35 psig. The railcar was stored on a siding during control valve monitored by a differential pressure
which time it was not monitored for temperature measurement. The nitrogen feed equipment was
or pressure. After 23 days of storage, the railcar installed on the ground level of the plant, which
exploded. Prior to the explosion, the railcars relief means that it was below the tops of the vessels.
valve lifted, and the immediate area was evacuated. Over time, EO and water (from the EO light ends
The exploding railcar created a large fireball and column feed vessel) condensed in the nitrogen
a crater in the ground. An adjacent operating line above the control valve. An EO-water mixture
facility was demolished. Twenty-eight people had gradually built up directly on the outlet of the
minor injuries but there were no fatalities. Based control valve, on the lower pressure side. Every
on the damage to the adjacent operating facility, time the control valve opened, the hydrostatic
the immediate evacuation most likely prevented a head forced a small amount of liquid EO and water
significant number of fatalities. to the upstream side of the control valve. The
nitrogen header became contaminated with liquid
As illustrated by the incident above, storage of EO/ EO, EO vapor and water.
water mixtures can present significant hazards.
Storage of EO/water mixtures in railcars, vessels or Nitrogen from this header was used to purge the
process equipment should only be practiced with a EO unit oxygen feed line during a unit shutdown.
thorough understanding of the reaction kinetics of During the purge, there was a reverse flow

Figure 5.9 Remnants of Railcar (after EO explosion caused by contamination with ammonia)

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5.0 Hazards of Ethylene Oxide

from the oxygen line into the nitrogen line. An 5.4 Ethylene Oxide
explosion between EO and oxygen occurred in the Decomposition Incidents
nitrogen line and a piece of shrapnel from the line
EO decomposes at a temperature around 932F
penetrated the adjacent ethylene line, releasing
(500C). The incidents listed below illustrate
ethylene into the pump house. The ethylene release
decomposition incidents.
resulted in a second, much larger explosion that
blew the door off and caused major damage to the Ethylene Oxide Decomposition Incidents
pump house.
and External Fires
An external fire is one of the most hazardous
5.3 Formation of Ethylene Oxide situations that can occur in an EO plant because
Vapor Clouds of the potential for EO decomposition. Even with
Release of EO vapors can result in the formation water spray systems and well-insulated equipment,
of a vapor cloud. Because the minimum ignition flame impingement from an external fire can
energy of EO in air is extremely low, EO vapor increase piping and vessel wall temperatures to EO
clouds often explode. (See Chapter 2 for more decomposition temperature in a short time period.
information on EO vapor ignition energy.) Note If this happens, an internal explosion can occur.
that in most EO contamination incidents and
EO decomposition incidents, the majority of the Fire Around Distillation Column
damage has resulted from an EO vapor cloud An EO producer in the U.S. had a rupture of an EO
explosion. Such incidents can be extremely compressor cylinder. This resulted in a large fire,
destructive. which engulfed the EO distillation column. The
resulting temperature increase on the surface of
Ethoxylation Plant Explosion the column and in the contained EO resulted in an
The contents of an ethoxylation reactor were internal explosion and significant damage.
pumped to a neutralization vessel about one half-
hour before completion of all the reaction steps. Flange Fire while Plant was Down
The neutralization vessel was located indoors. The A European EO producer experienced a flange
material was pumped to the vessel at a temperature leak in the EO distillation section of an EO plant.
of approximately 390F (199C). The vessel The plant had been shut down but still contained
contained 100 to 150 pounds of un-reacted EO. The an inventory of EO. The flange leak resulted
EO rapidly vaporized and escaped from the vessel, in a fire and the flame impinged on a process
mixing with the air in the building. An explosion line containing EO. The heat caused an EO
occurred when an operator entered the building to decomposition reaction to be initiated in the line.
turn on the ventilation system. The explosion killed The decomposition propagated down the line and
the operator entering the building, injured two other into a distillation column. The column head was
operators and destroyed the building housing the torn off and thrown about 100 feet. Large and small
ethoxylation reactor and the neutralization vessel. parts of the column jacket were scattered over a
Nearby buildings sustained extensive damage. 2000 foot radius. Only 7 minutes elapsed from the
start of the unit fire to the column explosion.

Pump Seal Leak Fire


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 an
EO decomposition in the minimum flow line. The
decomposition reaction propagated into the EO

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5.0 Hazards of Ethylene Oxide

purification column reflux drum where an explosion kept cleared of EO, pressured up with 200-psig
occurred. The reflux drum and its associated nitrogen, and left with the suction and double
distillation column were destroyed. This incident discharge valves blocked in. A small amount of EO
resulted in four fatalities. The plant was heavily leaked through the two blocked discharge valves
damaged and out of operation for four months. into the pump. An electrical system malfunction
caused the high-speed centrifugal pumps electric
Ethylene Oxide Decomposition Incidents motor to start. The pump ran blocked in for
and Mechanical Equipment approximately ten minutes until the seal area of the
Some important considerations regarding pumps pump reached EO decomposition temperature and
and compressors in EO service include the the pump exploded. The decomposition of the 0.6
potential for high temperatures if mechanical pounds of EO in the bowl of the pump generated
energy is not dissipated and the potential for a fire over 450,000 pounds of force and caused the
due to seal leaks. A good example of nondissipated failure of twelve, inch stainless steel nuts and
mechanical energy is a blocked pump discharge. bolts that held the pump together (Figure 5.10). The
The pump seal leak fire described immediately upper part of the vertical centrifugal pump and the
above is a good example of the potential motor (approximately 1000 pounds) were launched
consequences of a seal leak fire. The two incidents 60feet in the air. The pump and motor landed on
described in this section illustrate potential results the discharge piping of another EO feed pump that
of operating an EO pump deadheaded. was operating at 750 psig, pumping 80 gpm of EO
(Figure 5.11). The discharge piping did not fail.
Decomposition in Reflux Pump Propagates
to Reflux Drum and Tower Ethylene Oxide Decomposition
in Blocked-in Pump
The EO purification column reflux pump of a
European EO producer had been over-speeding. A U.S. EO producer uses magnetic drive pumps
The producer had also been experiencing extensively in EO service. At the time of this
instrumentation problems with the level controller incident, the magnetic drive pumps were protected
on the reflux drum, which caused the reflux control from overheating by a safety shutdown system
valve on the discharge of the reflux pump to fail that included shutdown initiators for both high
while closed. There was no minimum flow recycle temperature and low flow. During the normal
or high temperature or low flow safety shutdown startup sequence for these pumps, the shutdown
system on the reflux pump. (For more information system must be bypassed for a few seconds to
about safety systems on EO pumps, see section allow the low flow shutdown to be satisfied. To
6.7) The reflux pump operated deadheaded against allow the pump to start, the pump start switch was
the level control valve, causing the temperature also configured to function as a shutdown system
in the pump to rise. The EO vaporized and the bypass switch while it was depressed. During a
EO vapor was heated to its decomposition normal startup of these pumps, the operator had to
temperature. The EO in the pump decomposed hold the start switch down for a couple of seconds
and the decomposition propagated through the to allow the pump to start pumping and satisfy the
pump suction line into the reflux vessel where low flow shutdown.
an explosion occurred. Shortly afterward the EO On the day this incident occurred, an EO tower
purification column exploded. This explosion residue pump had been tripping every few
resulted in four fatalities. The plant was heavily minutes. An operator tried to start the spare pump,
damaged and out of operation for four months [6]. but it would not run. The operator then attempted
to re-start the pump that had tripped. The operator
Ethylene Oxide Decomposition in tried several times, but each time it tripped. In an
Blocked-in Pump attempt to keep the EO production unit running,
A U.S. EO producer used high-speed centrifugal the operator held the start button down for several
pumps to feed EO to two ethylene glycol units. minutes to keep the pump running without tripping.
The plant had a common spare feed pump for the After several minutes of holding the start button
two glycol units. The spare pump was typically down, the operator noticed that the pump had

28 Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007


5.0 Hazards of Ethylene Oxide

become very hot and there was a grinding sound decomposition; under EO decomposition conditions,
from the back of the pump. The operator released the methane produced in the decomposition can
the start button. The EO production unit was shut decompose further to form carbon and hydrogen).
down and the pump was pulled out for repair. The containment can had a blue discoloration that
When the pump was opened up for repair, the area indicated that it had been exposed to temperatures
between the driven magnet and the containment over 800F (426C). EO had decomposed inside the
can was completely packed full of carbon (carbon containment can and around the driven magnet [7].
deposits are sometimes found after an EO In this incident, it is believed that the decomposition
reaction did not propagate through the small
passages inside the pump because the mass of
the metal in the pump absorbed enough heat to
Figure 5.10 High Speed Centrifugal Pump quench the decomposition flame.
Launched by Decomposition
of 0.6 Pounds of Ethylene Oxide Ethylene Oxide Decomposition
Incidents and Leaks

Under Insulation
An EO leak into porous insulation can result in
reactions of EO with the insulation material or EO
with moisture contained in the insulation, which
can lead to high temperatures. This may occur with
mineral wool, asbestos, fiberglass, calcium silicate,
magnesium silicate and other porous insulation
materials. Porous insulation can soak up and retain
water from the environment, thereby providing a
large surface area for EO-water contact. It has also

Figure 5.11 Motor Landed on Operating Ethylene Oxide Pump Discharge Line

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5.0 Hazards of Ethylene Oxide

been shown that many types of insulation catalyze increased both the temperature and the pressure
reactions of EO [8]. These reactions all produce in the tower until it ruptured. The remaining EO in
heat, the dissipation of which is inhibited by the the tower was suddenly released at high pressure
insulation itself. An under insulation EO leak can and temperature forming an EO vapor cloud, which
result in a hot spot on the wall of the vessel, then exploded. The EO vapor cloud explosion
which can trigger a decomposition reaction of the caused more damage to the plant than the initial
EO inside the vessel. Use of nonporous insulation, decomposition reaction (Figures 5.12, 5.13, 5.14,
such as cellular glass, reduces the potential for hot 5.15).
spots and still provides a degree of protection from
overheating due to fire. See Section 6.3 for a more Ethylene Oxide Leak Under Insulation
thorough discussion of insulation. Results in Tower Explosion
In 1989, a catastrophic explosion of an EO
Ethylene Oxide Leak at an Insulated Manway purification column occurred at the production
Flange Results in Tower Explosion plant of a European EO producer. A crack
In 1987, a European EO producer had a catastrophic developed where a pipe was attached to the wall
explosion of its EO purification column. The of an EO distillation tower. The crack allowed EO
damage to the plant was very extensive. to leak into mineral wool insulation. EO reacted
Investigation after the incident revealed that a with water in the insulation to produce polyglycols.
manway flange leak under mineral wool insulation When portions of the insulation and insulation
on the EO distillation column resulted in an external jacketing were removed for maintenance, air flowed
hot spot which caused an EO decomposition into and under the insulation, rapidly oxidizing the
inside the tower. The decomposition reaction polyglycols and producing a high temperature.

Figure 5.12 Ethylene Oxide Distillation Column Reboiler after Explosion

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5.0 Hazards of Ethylene Oxide

Figure 5.13 Aerial View of Ethylene Oxide Plant after Explosion

Figure 5.14 Remnants of Base of Ethylene Oxide Distillation Column after Explosion

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5.0 Hazards of Ethylene Oxide

Figure 5.15 Piece of Ethylene Oxide Distillation Column Wall Turned Inside Out by Explosion

The insulation prevented dissipation of the heat [9]. After the incident, the EO producers research
and the reaction in the insulation caused the identified a previously unknown reaction of EO:
wall temperature of the EO distillation tower disproportionation (see discussion in Section 2.3).
to reach EO decomposition temperature. The This reaction can be initiated at significantly lower
internal decomposition reaction resulted in vessel temperatures than thermal decomposition. In this
failure. In this incident, the EO decomposition incident, the reaction occurred
reaction initiated in the aldehyde column and Inside the tubes of a distillation column reboiler;
propagated through overhead piping to the EO
In the presence of a deposit of high surface
purification column, which also exploded. Like
the incident in 1987, most of the damage to the area rust embedded in an EO polymer matrix;
plant in this incident was caused by the EO and
vapor cloud explosion. Damage to the plant was During a period when flow through the reboiler
severe, requiring more than a year for rebuilding was reduced by a process upset resulting in
(Figures5.16, 5.17, 5.18). tube surfaces exposed to vapor only, not liquid.
It was concluded that loss of reboiler circulation
Ethylene Oxide Decomposition
allowed for rapid heat buildup in the vicinity of the
Ethylene Oxide Disproportionation Reaction
iron oxide/polymer deposit, resulting in localized
in Column Vertical Thermosiphon Reboiler
EO vapor temperatures reaching the thermal
Ethylene Oxide Redistillation decomposition temperature. The result was an
explosion that destroyed the distillation column.
Column Explosion
An EO manufacturer experienced an explosion in Ethylene Oxide Decomposition
an EO redistillation column (Figures 5.19, 5.20). The Ethylene Oxide Disproportionation Reaction
explosion appeared to have been initiated at the in a Horizontal Thermosiphon Reboiler
top of the reboiler. There was one fatality and the
This June 2000 redistillation column incident
plant was out of service for more than one year
32 Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007
5.0 Hazards of Ethylene Oxide

Figure 5.16 Aerial View of EO Unit After Explosion

Figure 5.17 EO Plant Burning after Explosion

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5.0 Hazards of Ethylene Oxide

Figure 5.18 EO Purification After Explosion Two Towers are Missing

occurred on the shell side of a horizontal There was inadvertent heat input to the reboiler
thermosiphon reboiler. Damage was limited to the during startup;
trays in the column and some associated piping. The initial charging of EO to the column during
There was no loss of containment and there were startup was interrupted, exposing the reboiler
no injuries or fatalities. The incident occurred tube bundle to EO vapor;
during the startup of the unit and when the
An iron oxide-polymer deposit was present
following conditions were present:
on the reboiler tubes which initiated the
disproportionation reaction.
Figure 5.19 Ethylene Oxide Re-distillation
Tower Explosion (re-distillation
tower is gone and adjacent
tower is damaged and leaning) Figure 5.20 Resulting Damage to the Plant

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5.0 Hazards of Ethylene Oxide

The iron oxide-polymer deposit was wetted and 5.5 Ethylene Oxide
dried during the startup with the interruption Transportation Incidents
of feed to the column. A rapid temperature rise
In both of the following transportation incidents an
initiated the disproportionation reaction, which in
EO railcar was punctured and a fire resulted. In one
turn led to an EO vapor decomposition reaction.
incident, the emergency responders controlled the
The decomposition reaction propagated from the
process of burning off the EO. In the other incident,
reboiler into the distillation column. Several of
injuries were prevented by evacuation.
the bottom trays in the column did not have the
manways in place. This allowed the velocity of Ethylene Oxide Railcar Fire
the reaction front and volume of decomposition
gases to accelerate to a critical point up to the In July 1981, a full railcar of EO was punctured as
trays which had the manways properly installed. a result of a coupler override (this was before
The remaining trays in the top of the column were double shelf couplers were required by federal
propelled upward and wedged in the top of the regulations) at a railyard in Newark, New Jersey.
tower and the vapor overhead line. The pressure The leaking EO ignited. The location of the railyard
wave continued into the column overhead piping was very close to the Newark International Airport
damaging several piping supports and several and the New Jersey Turnpike. Both the airport
trays in the downstream column. The top trays were and a four mile section of the turnpike were shut
forced into the overhead piping of the column. It is down during the incident. Three unmanned fire
believed that the trays compacted into the top of monitors were set up to limit the temperature
the tower and that overhead piping prevented the increase in the car and to reduce the likelihood
decomposition reaction from propagating into the of a hot spot in the car shell. Nitrogen was fed
downstream equipment. into the car through a hose from portable nitrogen
bottles to maintain an inert atmosphere inside the
Ethylene Oxide Decomposition car. With input from EO technical specialists, a
Catalyst Residue in the Vapor Space burn pit was set up approximately 400 feet away
of an Ethoxylation Reactor from the railcar. Liquid from the railcar was routed
to the burn pit and ignited. The contents of the
An ethoxylation reactor exploded during normal
railcar were burned over a three hour period while
operation while EO was being fed to the reactor.
the leaking EO continued to burn at the railcar.
During the investigation of the explosion, pieces
A 1 inch firewater hose was also connected to
of the reactor head were found that had a heavy
allow flooding of the cars interior when the flaring
buildup of potassium hydroxide (KOH) catalyst
was complete. The fire was allowed to burn until
on the metal. The reactor was not designed for
all liquid EO had been consumed. When the fire
addition of KOH directly into the liquid. The liquid
went out, the car was filled with water as rapidly as
KOH stream was added at the top of the reactor
possible to cool the car and to expel unburned EO
and a KOH residue had built up on the inside of
vapors. No further damage resulted.
the head. The KOH catalyzed a reaction of the
EO in the vapor space of the reactor driving the Ethylene Oxide Railcar Explosion
temperature in localized areas of the reactor head
In October 1969, a multi-car derailment resulted
to the decomposition temperature. The vapor
in the puncture of an EO railcar and a fire. Water
space decomposed explosively. The vapor space
was put on the burning railcar and on an adjacent
of the reactor was blanketed with nitrogen, but the
EO railcar that was not leaking. The fire was
nitrogen partial pressure was insufficient to yield
extinguished after about 12 hours. About five hours
a non-decomposable mixture. Refer to Section6.6
after the fire was out, the safety relief valve on the
for more information on inerting ethoxylation
adjacent EO railcar lifted and vapor from the relief
reactors.
valve caught fire. Comments from responders at
the scene indicated that the adjacent car felt
cool after the initial fire was extinguished. At this
point, the accident scene was cleared for a radius
of mile. After about 55 hours, the relief valve
fire went out for a brief period and then a violent

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5.0 Hazards of Ethylene Oxide

explosion occurred. A large piece of the railcar was Figure 5.21 Filter Case after Runaway
blown 5,000 feet through the air. The explosion Polymerization
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 Ethylene Oxide


Polymerization Incidents
Polymerization Incidents in
Ethylene Oxide Filters
In 1969, a U.S. EO producer had an EO filter explode
due to runaway polymerization. The filter had been
left full of EO and blocked-in.
In May 1998, runaway polymerization occurred in
an EO railcar-loading filter of a U.S. EO producer.
The insulated loading filter was normally cooled
by continuous circulation of chilled EO. However, Figure 5.22 Filter Case after Runaway
circulation in this case had been stopped for
Polymerization
over two days due to maintenance on other
equipment in the EO tankfarm. During the incident
investigation, it was discovered that the filter
elements had not been changed in 18 months and
were highly loaded with rust. The person formerly
responsible for changing the filter elements had
retired and this duty had not been reassigned to
another employee.
The ambient temperature at the time of the
runaway polymerization incident was 100F (38C).
The combination of the stagnant EO, the high
ambient temperature and the rust in the filter
elements initiated the polymerization. The filter
case did not rupture, but the temperature in the Figure 5.23 Filter Case after Runaway
filter case was very high and the pressure was Polymerization
high enough to stretch the bolts on the head of
the filter case. The cotton filter elements were
found to be carbonized (dehydrated), indicating
that the temperature in the center of the filter case
exceeded 500F (260C) (Figures 5.21, 5.22, 5.23).

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 circulation
line was also used for addition of a KOH catalyst.
In order to continue feeding EO to the reactor, the

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5.0 Hazards of Ethylene Oxide

operator had to reset the high temperature EO incidents caused damage to the plants. Most of
feed shutdown. When it was discovered that the the facilities involved used oxidizers to control EO
circulation line was blocked, the block valve was emissions. In April 2000, in response to these
opened to re-establish cooling, but this action explosions, the National Institute for Occupational
allowed a slug of concentrated KOH to enter the Safety and Health (NIOSH) published a Safety
reactor and come into contact with EO. Because Alert titled Preventing Worker Injuries and Deaths
catalyst was not present when EO feed was from Explosions in Industrial Ethylene Oxide
started, the EO concentration exceeded normal Sterilization Facilities. [10] EPA and Industry
design levels. The sudden addition of catalyst representatives from the Ethylene Oxide Sterlizers
when the cooling line was opened resulted in Association (EOSA) collaborated with NIOSH to
a runaway reaction. Subsequently, the reactor produce this alert. It warns EO sterilization facility
ruptured explosively. Metal parts and valves employees and managers about the explosion
were propelled over a distance of approximately hazards associated with oxidizers, and it makes
2,300feet. comprehensive recommendations for preventing
future incidents.
Inadvertent Addition of Reactive Material
During 1997 and 1998, there were explosions and
(Hydrogen Peroxide)
fires at four large-scale sterilization plants that use
The reactor in a European ethoxylation unit EO to sterilize medical devices. There was another
suddenly exploded. The incident investigation explosion at large-scale sterilization plant in 2004.
revealed that hydrogen peroxide used to bleach The explosion in 2004 was investigated by the U.S.
the ethoxylate product was inadvertently added Chemical Safety and Hazard Investigation Boar
during the EO addition phase of the operation. The (CSB). The CSB produced a report and video on
EO reacted with the hydrogen peroxide and caused the 2004 explosion, which is available to the public
the reactor to explode. There was no interlock to on the CSB website, www.csb.gov.[11]
prevent addition of hydrogen peroxide when EO
All of the sterilizer explosions in 1997, 1998
was present in the reactor.
and 2004 were associated with EO abatement
devices used for destruction of EO in process
5.8 Incidents in Ethylene Oxide vents. Four of the explosions involved catalytic
Abatement Devices oxidizers and one explosion involved a thermal
oxidizers. Each of the explosions either severely
Catalytic and Thermal Oxidizer Incidents damaged or destroyed the EO abatement device
Between 1994 and 1998, EO was involved in 10 and the sterilization chambers. Figure 5.24 is an
explosions at industrial EO sterilization facilities overview diagram of the 2004 explosion. Figure
and EO repackaging plants. One of these 5.25 through 5.27 are photos of damage to the
incidents resulted in a fatality and all of the sterilization plant. [11]

Figure 5.24 Diagram of


Sterilizer
Explosion

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5.0 Hazards of Ethylene Oxide

Two of the sterilizer incidents occurred during the Figure 5.25 Sterilizer Explosion Damage
startup testing of catalytic oxidizers. In one of the
incidents, there was an explosion with a fireball
and the oxidizer system and the building were
destroyed. In the 2004 explosion, the doors were
blown off of the sterilization chamber and the walls
of the chamber itself were bulged outward. [11]
Three common themes in all of these EO
abatement device incidents were: (1) the lack
of an interlock to prevent opening the chamber
door when EO was in the chamber or the ability
for the operator to override an interlock, (2) a
higher than design concentration of EO at the
inlet of the EO abatement device, and (3) the lack
of EO concentration monitoring in the sterilization
chamber to warn of explosive concentrations.
Catalytic oxidizers are designed for conversion
of low concentrations of EO in a vent stream to
carbon dioxide and water. When the vent system Figure 5.26 Sterilization Chamber Damage
to a catalytic oxidizer has a higher then design EO
concentration, the result can be overheating of
the catalyst bed and uncontrolled combustion or
decomposition of the excess EO due to the high
temperature in the catalyst bed.

Overload of Reactive Vent Scrubber


Incidents have also occurred in acid or caustic
reactive EO vent scrubbers when a higher than
design EO concentration was sent to the scrubber.
Sending liquid EO to a reactive vent scrubber can
easily overload a scrubber. Reactive vent scrubbers
are typically designed to handle low concentrations
of EO in a gaseous vent stream. Reactive vent
scrubber systems are often designed with acid or
caustic recirculation systems. If liquid EO is fed
into the bottom of a reactive vent scrubber, it can
flow into the acid or caustic vessel and result in a Figure 5.27 Damage to the building wall from
runaway reaction and explosion. impact of sterilizer door
In the early 1990s, operators at an ethoxylates
production unit with a sulfuric acid scrubber tried
to clear the units EO feed line by blowing the liquid
EO to the vent scrubber with nitrogen. The liquid
EO overloaded the vent scrubber, resulting in a
runaway EO hydrolysis reaction in the scrubber. The
polypropylene packing in the scrubber melted and
the 40 foot tall fiberglass reinforced plastic (FRP)
scrubber tower failed and collapsed due to the
high temperature produced by the EO hydrolysis in
the scrubber. See Section 6.8 for more information
on vents and scrubbers.

38 Ethylene Oxide Product Stewardship Guidance Manual Copyright May 2007