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Introduction
1.0
Benzoyl Peroxide Properties and
Applications
Table 1
NFPA Peroxide Classifications
Peroxide BPO
Hazard Class Characteristics Concentrations
I Capable of deflagration but not 98% granular
detonation (a)
II Burns very rapidly, presents a 78% granular
moderate reactivity hazard
III Burns in the same manner 75% granular
as ordinary combustibles,
presents a minimal reactivity hazard
IV Burns with less intensity 50% paste
than ordinary combustibles or
does not sustain combustion,
presents no reactivity hazard
(a) A deflagration is a reaction that propagates at less than the speed of sound and, with
confinement, can result in an explosion. By comparison, a detonation is a reaction that
propagates at greater than the speed of sound and results in an explosion regardless
of confinement. Detonations have a much greater destructive potential than
deflagrations.
Table 2
Characteristic Properties of 98 Percent Granular BPO
2.0
Catalyst Systems Operations
w
is a subsidiary company of Alco
A 98 percent granular BPO prod- Catalyst Systems
Industries. U.S. Chemical and Plas-
uct is also made in the paste room
tics formulates and manufactures
by drying batches of purchased 75 began producing
repair, appearance, and mainte-
percent granular BPO using a 98 percent
nance products for the marine and
spherical rotating vacuum dryer.
aviation industries and the automo-
The 98 percent product is packaged granular BPO
bile aftermarket. These products
into 1-pound bags. 5 years ago for
include a variety of putties, fillers,
waxes, compounds, paints, coatings, Catalyst Systems began producing the rubber, marine,
catalysts, and adhesives. 98 percent granular BPO 5 years
ago for the rubber, marine, and and printed circuit
Twenty-five people are employed at
printed circuit board industries. board industries.
the facility in Gnadenhutten, Ohio.
This product was initially manufac-
A portion of this staff supports
tured by air-drying 75 or 78 per-
Catalyst Systems operations, while
cent BPO granular products in
the remainder is dedicated to other
open metal pans in an oven over
activities of U.S. Chemicals and
several days. Because the process
Plastics.
The plant site has two buildings
(Figure 1). Building 1 contains
offices, a quality control laboratory, Figure 1
a shop, storage areas, and a paste
filling and packaging area. Building Catalyst Systems, Inc., plant site
2 was constructed in 1977 and is
used solely for BPO production. It
is divided into a manufacturing area
Building 2 Building 1
and a paste room.
In the manufacturing area, raw
materials are added to a reactor to
produce 20 percent BPO—which
is then sent through a centrifuge,
where water is removed. The
resulting product is 78 percent
granular BPO. Some of this
material is packaged in drums for
6
was both time consuming and sub- equipment and placed it in the
ject to quality problems (i.e., the northwest corner of the paste room
metal pans rusted and contaminated (Figure 3).
the finished product), Catalyst
The vacuum dryer was loaded
w In June 2001,
Systems determined that vacuum
drying was more economical and
through a feed port with 200 pounds
of 75 percent BPO. Hot water (ap-
Catalyst Systems maintained the required quality
proximately 82°C) was circulated
control.4
purchased a used through the dryer’s jacket to indi-
In June 2001, Catalyst Systems rectly heat the BPO. The dryer
double-cone purchased a used double-cone rotated slowly, causing the BPO to
vacuum dryer, vacuum dryer, which was jacketed tumble and evenly heat, minimizing
and glass-lined (Figure 2). Mainte- the production of hot spots.
which was nance personnel installed the
The atmosphere in the dryer was
jacketed and placed under vacuum. As the BPO
glass-lined. was heated, the vacuum system
4
When a system is dried under vacuum, the pulled air and water vapor from in-
temperature at which water evaporates is
lower—which allows the material to be dried side the dryer through a polypropy-
at a lower and usually safer temperature. lene bag filter, then a separator, and
Figure 2
Catalyst Systems vacuum drying system
(8.7-ft3 working capacity dryer and associated piping/equipment)
In Out
Automatic
V3 Valves
V1 = fail closed
V1 V2 V2 = fail closed
Polypropylene V3 = fail open
bag filter
Vacuum line
Temperature probe
Separator
3.0
Incident Description
w Because it 3.1
Pre-Incident Activities to be 97 percent BPO, which was
typically took within the range expected. The
drying system was started.
O
2.5 days to dry n Friday morning, Decem-
75 percent ber 27—6 days before the At about 8:50 am, operators heard
incident—Catalyst Systems employ- the hot water valve close, indicating
material to ees began normal procedures to that the temperature inside the
98 percent, prepare a batch of 98 percent BPO. dryer had reached 42°C. They
The vacuum dryer was loaded with then closed a manual valve on the
operators 200 pounds of granular 75 percent hot water line to ensure that the
anticipated that the BPO and started. As per practice, hot water did not automatically re-
hot water to the dryer was shut off start. The dryer continued to
batch would be at about 2:00 pm to allow the mate- rotate under vacuum to allow the
ready after rial to cool. At approximately material to cool. Operators
3:30 pm, the entire drying system planned to resample the material
completing one was shut down for the day. Because after lunch to determine if it had
drying cycle [on] the plant did not operate over the reached the desired concentration
weekend, the drying system re- of 98 percent.
the morning [of mained off and sealed on Saturday
January 2]. and Sunday.
3.2
On Monday morning, December 30, The Explosion
operators followed normal proce-
dure to restart the drying system.
At 11:30 am on January 2, the
The drying process described above
operators took their lunch break at
was repeated. On the following 2
a table located in the Building 2
days—plant holidays—the drying
paste room (Figure 3). One of the
w At 11:55 am, the
system was not operated, and the
dryer remained sealed.
operators noted an unusual noise
coming from the vacuum pump,
vacuum dryer Plant personnel returned to work on which he planned to check after
suddenly January 2, 2003. Because it typi- lunch. At 11:55 am, the vacuum
cally took 2.5 days to dry 75 percent dryer suddenly exploded while the
exploded . . . material to 98 percent, operators operators were still seated at the
anticipated that the batch would be lunch table.
ready after completing one drying
The employees described thick
cycle in the morning. The dryer
black smoke with rolling flames and
was opened and sampled at approxi-
a loud boom. They quickly exited
mately 8:00 am. The plant labora-
the building and went to the
tory determined the concentration
designated evacuation area. One
9
w
called to assist.
well as the dividing wall, were ex- The dryer was
Following the advice on the material tensively damaged (Figure 6). The
safety data sheet (MSDS) for BPO, building’s primary structural propelled
the fire department continued to frames were intact, though the roof through the
put water on the building and its decking and supports in the south-
contents. Runoff water leaving the west corner were badly damaged. corrugated steel
property was tested at several dividing wall . . .
6
Tests were performed to determine pH as
well as the presence of oxidizers, fluoride,
petroleum products, organic solvents, iodine, and through
bromine, and chlorine.
several pallets
of filled fiber
Figure 4 drums.
Damage to Catalyst Systems BPO production building
Figure 5
Filled fiber drums damaged by dryer
Figure 6
Building damage, southwest side
11
4.0
Potential Initiating Scenarios
w
bag of 98 percent BPO is 68°C.8
temperature or pressure; it was Because SADT is dependent on the BPO may
primarily manually controlled. size and type of package, it would
Because the drying system was
decompose
be lower for the 200-pound batch
extensively damaged and there that was being processed in the violently when
was little recorded information, dryer.
it was not possible to determine
exposed to
Half-life data suggest that half of
exactly what initiated the explo-
the 98 percent BPO in the dryer
excessive heat,
sion. However, CSB identified
several potential scenarios by
would have decomposed in about 3 shock, or friction.
hours at 82°C.9 To maintain an
examining and testing physical
appropriate factor of safety below
evidence, interviewing employ-
SADT, another manufacturer’s
ees, and reviewing system
literature suggests that 1-pound
documentation.
bags of 98 percent BPO should not
BPO may decompose violently be stored at temperatures higher
when exposed to excessive heat, than 38°C.10 Clearly, the BPO dry-
shock, or friction. Contaminants
may initiate the decomposition
ing system at Catalyst Systems was
running very close to the thermal w Clearly, the BPO
reaction, which produces a large decomposition temperature for 98 drying system . . .
volume of gas. Each of these percent BPO, which was the likely was running
hazardous conditions was poten- cause of the explosion.
tially present in the BPO drying very close to
system.
the thermal
The drying system was designed
decomposition
to use 82°C water to heat the
material in the dryer to approxi- temperature for
mately 42°C, at which point the SADT is the temperature at which a perox- 98 percent BPO,
7
water was shut off by closing the ide undergoes a rapid and violent decomposi-
tion, and may self ignite.
valve that supplied the dryer’s which was the
8
The SADT for a 1-pound bag of 98 percent
jacket. However, the jacket was BPO is listed in various manufacturers’ likely cause of the
not designed to be drained; the MSDSs.
water remained in the jacket at
9
Degussa Corporation general technical in- explosion.
formation. Half-life indicates the time in
82°C until it was cooled by heat which half of the original quantity of perox-
losses to the surrounding ide will decompose at a given temperature.
Under adiabatic conditions, where no heat is
environment. lost from the vessel, the half-life time is de-
creased.
10
Atofina, Organic Peroxides—Their Safe
Handling and Use, 2001.
12
5.0
Standards and Guidance
w
guidance documents describe peroxides should be isolated from
the hazards of organic peroxides storage areas, other equipment, It is not possible
and recommended practices for and work areas. Buildings that to suggest an
storage and handling. Some of house manufacturing equipment
these documents also contain should be built with fire- and exact temperature
specifics on BPO. In addition, a explosion-resistant walls with at which BPO will
number of trade groups, insurance adequate capabilities to vent
companies, and government agen- pressure. decompose;
cies have published books, research however, at higher
w Safeguards should be in place to
reports, and technical papers, as
protect against the possibility of temperatures, the
listed in Section 9.0, Annotated
exposing BPO to ignition sources,
References. decomposition
friction, and shock. Electrical
A review of standards and guidance equipment in areas with open reaction takes less
suggests that several commonly containers of BPO should be
accepted practices would have sig- classified according to Class I, time to start and
nificantly reduced the likelihood of Division 1, of Article 500 of the proceeds more
the explosion at Catalyst Systems, National Electric Code; and all
as noted below: equipment should be adequately rapidly.
w Safeguards should be in place to grounded.
avoid overheating BPO. The w BPO generates large volumes of
SADT is reported as 68°C for gases during decomposition and
1-pound plastic bags. Manufac- should not be confined. Addition-
w
turers and users should recog- ally, precautions should be taken
nize that these data are specific to avoid contamination, which BPO generates
to the package size and charac- may initiate the decomposition large volumes of
teristics, which are determined reaction.
by testing. It is not possible to gases during
These good practices—discussed
suggest an exact temperature at decomposition
throughout the standards and guid-
which BPO will decompose; how-
ance documents—do not represent a and should not be
ever, at higher temperatures, the
complete set of practices for BPO
decomposition reaction takes less confined.
handling. However, if they had been
time to start and proceeds more
in place, they may have reduced the
rapidly. Safe temperatures
potential for the explosion.
should be chosen for specific
systems, and temperature con-
trols and alarms should be in-
stalled accordingly.
14
6.0
Management of Chemical Process Safety
w
reactants and products.
. . . The prevent catastrophic incidents. It
is considered to be good practice in w Thermal and chemical stability
development, operations that handle and process data for reactants and products.
understanding, hazardous materials. In Guidelines
w Process chemistry and technol-
for Technical Management of
and application of ogy information.
Chemical Process Safety, the
process safety American Institute of Chemical w Equipment design temperature
Engineers (AIChE) Center for and pressure.
information during Chemical Process Safety (CCPS) w Range of process temperature
process design describes 12 core elements of a and pressure.
good process safety management
was inadequate system. w Equipment and materials of con-
for managing struction specifications.
Catalyst Systems did not have a
the explosive process safety management pro- w Material and energy balances of
gram in place, nor were employees the chemical process.
decomposition trained in the use of these manage- w Safety systems (e.g., interlocks,
hazard of ment systems. Deficiencies in pressure relief systems, detec-
certain elements, as discussed tion or suppression systems).
98 percent BPO. below, significantly contributed to
the January 2 incident. w Operating procedures and train-
ing information.
w Design codes and regulatory
6.1
standards.
Process Knowledge
and Documentation All of this information should be
compiled, analyzed, and updated
before beginning design and con-
A process safety management
struction, and then kept up to date.
system for chemical manufacturing
The information should be readily
is only as good as the foundation
available to employees.
upon which it is built—the actual
research, development, design, At Catalyst Systems, the develop-
construction, and operational data. ment, understanding, and applica-
Basic process safety information tion of process safety information
includes the following: during process design was inad-
equate for managing the explosive
15
11
An increase in volume changes the ability Catalyst Systems had no documentation
12
of the substance to cool because of differ- describing the type of grease used in the
ences in surface area. sealed bearing.
16
w
intended. The frequency of testing At Catalyst Systems, operators
Although the should be based on known failure received on-the-job training only.
history, manufacturer’s recommen- Although the operators appeared to
operators dations, and operating experience. have good knowledge of normal
appeared to have A preventive maintenance program
operation, there were no written
procedures and no structured
good knowledge should also have included the glass
training. In addition, there were no
lining inside the vacuum dryer.
of normal Interviews with operators revealed
procedures for abnormal situations.
Catalyst Systems should have iden-
operation, there that a chip had developed in the
tified unusual scenarios and trained
lining. Granular BPO may have be-
were no written come lodged in this chip and over-
operators on response actions, such
as what to do about finding a chip in
procedures and no heated (because it was now closer to
the dryer’s glass lining, hearing un-
the jacket and heated to a higher
structured training. temperature than the rest of the
usual noises from the vacuum
pump, or detecting abnormal pro-
batch), creating a hot spot. More-
cess conditions.
over, the metal under the glass lin-
ing provided a potential source of
contamination. Catalyst Systems
should have developed procedures
for inspecting the glass lining and
making repairs when necessary.
19
7.0
Regulatory Analysis
13
See www.osha.gov.
14
OSHA Director, Directorate of Compliance
Programs, letter re HHCs as applied to how
high the percentage of a chemical must be to 17
The rationale for OSHA threshold quanti-
require compliance, April 14, 1993. ties is discussed in a 1996 memo prepared by
15
OSHA Deputy Director, Directorate of Thomas H. Seymour, Directorate of Safety
Compliance Programs, letter re HHCs as ap- Standards Programs, “Rationale for Pre-
plied to threshold quantity, April 24, 1994. amble, Appendix A, Chemical List.”
16
The approximate amount of 98 percent 18
In its regulation, the State’s objective was
BPO onsite on the day of the explosion was to protect people in the vicinity of a cata-
2,140 pounds. strophic release beyond a facility boundary.
20
T
blast origination is determined he January 2 explosion at
such as the one at using an empirically derived Catalyst Systems was most
function method based on equiva-
Catalyst Systems likely caused by a thermal decom-
lent mass of trinitrotoluene position of 98 percent BPO. Other
can be very (TNT). possible causes or contributors in-
hazardous to Although there were no serious in- clude contamination, static electric-
juries on January 2, explosions such ity, or friction.
workers who may
as the one at Catalyst Systems can The hazards of BPO are well known
be closer than be very hazardous to workers who and documented. Catalyst Systems
may be closer than 100 meters to should have reviewed consensus
100 meters
the origin. Because of the potential standards and guidance documents
to the origin. hazard, good practices must be fol- on the handling, storage, and manu-
lowed even when handling small facture of BPO, and implemented
amounts of a hazardous chemical their recommended practices.
such as BPO.
Dry BPO is hazardous in any
OSHA investigated the Gnaden- quantity. Regardless of OSHA PSM
hutten plant following the January 2 coverage, companies should imple-
w Catalyst Systems incident. For violation of the Gen-
eral Duty Clause (Section 5(a)(1) of
ment good engineering practices
when working with BPO, such as
should have the Occupational Health and Safety gathering relevant hazard informa-
Act of 1970), OSHA issued a cita- tion, reviewing reactive hazards,
reviewed con-
tion with willful violation to Catalyst developing a preventive mainte-
sensus standards Systems for not following the good nance program, and developing and
practices outlined by the principles conducting training on operating
and guidance
of process safety management. procedures for normal and abnor-
documents on the mal situations.
handling, storage, If Catalyst Systems had reviewed
and manufacture and followed industry standards
and guidance documents, and
of BPO, and implemented good engineering
implemented their practices to manage the hazards, it
is likely that this incident would not
recommended have occurred.
practices.
21
9.0
Annotated References
Code for the Storage of Organic Guidelines for Technical
Peroxide Formulations, NFPA 432 Management of Chemical Process
The National Fire Protection Safety, American Institute of
Association (NFPA) began Chemical Engineers (AIChE)
developing codes for the storage Center for Chemical Process Safety
of organic peroxides in 1969; (CCPS)
the current standard was The CCPS chemical process
published in 2002. NFPA 432 safety management system
applies to storage only and focuses on management systems,
excludes manufacturing. The along with technological
standard defines hazard advances, as essential to prevent
classifications for organic catastrophic incidents. This
peroxides based on the book, published in 1989,
characteristics of available describes the 12 core elements
peroxide formulations and a necessary for a complete
limited number of full-scale fire process safety management
tests. program. These practices are
recognized throughout the
Fire, Explosion, and Health
chemical industry.
Hazards of Organic Peroxides,,
American Insurance Association “Hazard Evaluation of
Research Report No. 11 Dibenzoylperoxide (BPO),”
discusses problems associated Proceedings, 17th International
with the use of concentrated Pyrotechnics Seminar–2nd Beijing
organic peroxides, classification International Symposium on
and evaluation, fire and Pyrotechnics and Explosives
explosion hazards, and typical In this scientific technical paper,
fires and explosions; and from Volume 2 of the 1991
includes precautionary proceedings (pp. 993-998),
recommendations. This 1966 authors Tadao Yoshida and
report reviews case histories of others describe an explosion in a
eight BPO explosions and fires manufacturing factory in Tokyo
in transportation, laboratory, in 1990, including the results of
and manufacturing several experiments on the
environments. hazards of dry and 75 percent
water-wetted BPO. The authors
conclude that—unlike dry
BPO—75 percent BPO diluted
22
CSB is an independent Federal agency whose mission is to ensure the safety of workers,
the public, and the environment by investigating and preventing chemical incidents. CSB
is a scientific investigative organization; it is not an enforcement or regulatory body.
Salus Populi Est Established by the Clean Air Act Amendments of 1990, CSB is responsible for
Lex Suprema determining the root and contributing causes of accidents, issuing safety recommen-
dations, studying chemical safety issues, and evaluating the effectiveness of other
People’s Safety government agencies involved in chemical safety.
is the Highest Law No part of the conclusions, findings, or recommendations of CSB relating to any chemical
incident may be admitted as evidence or used in any action or suit for damages arising out
of any matter mentioned in an investigation report (see 42 U.S.C. § 7412(r)(6)(G)). CSB
makes public its actions and decisions through investigation reports, summary reports,
safety bulletins, safety recommendations, case studies, incident digests, special technical
publications, and statistical reviews. More information about CSB may be found at
www.csb.gov.