Toxic Gas Release Caused by the
Thermal Decomposition of a Bulk
Powder Blend Containing Sodim
DichloroisoCyanmte
Andrew R. Carpenter,RE. and Russell A. Ogle
Exponent, Two North Riverside Plaza, Suite 1400, Chicago, IL 60606; acarpenter@exponent.com(primary author)
A thermal runaway reaction occurred during the mixing
of a batch of a bulkpowder that resulted in theproduction
and release of toxic gases. The mixture consisted of an oxi-
dizer (sodium dichloroisocyanurate), some organic com-
pounds, and inert compounds. This toxic release led to the
evacuation of the building and resulted in extensive damage
to thefacility. This was only thefourth time an 1,100-pound
batch of this material had been mixed in this equipment.
Prior to thisproduction run, the material had beenprepared
in small batches of 2 to 50 kilograms. Accelerated Rate
Calorimetry (ARC) testing had been performed prior to the
scale-up to production batches.
Thispaper look into the root causes of thisparticular acci-
dent and demonstrates howproper anulysis of the testing data
and other warning signs observed during the bench testing
could haw reuealed the likelihood of this accident.Further; this
pper will consider how simple design changes to the manufac-
turingproces resulted in an inherentlysafer&@.
INTRODUCTION
A reactive material is a substance that can liberate
sufficient energy for the occurrence of a hazardous
event. This case study describes an accident in which
a reactive material, sodium dichloroisocyanurate (CAS
No. 2893-78-9), was blended with both organic and
inert ingredients. During the blending process, an
unintended chemical reaction occurred. This unin-
tended chemical reaction released (suspected) chlo-
rine gas into the production facility. The gas release
caused the evacuation of operations personnel, shut-
down of the facility, and extensive equipment and
property damage. An investigation was conducted to
determine the cause of the accident.
The methodology of this investigation was based
primarily on two guidance documents: NFPA 921
Process Safety Progress (V01.22, No.2)
Guidefor Fire and Explosion Investigations, published
by the National Fire Protection Association (NFPA) ill,
and Guidelinesf o r Investigating Chemical Process
Incidents [21, published by the Center for Chemical
Process Safety (CCPS) of the American Institute of
Chemical Engineers (AIChE).
The scope of the investigation was to determine
what happened, why it happened, and what lessons
could be learned to prevent a similar event from
occurring again. The “Background” section describes
the chemicals used and the production process. The
“Investigation” section describes hypotheses for the
cause of the incident and the examination, research,
and testing performed to evaluate them. The “Analysis
of Potential Initiation Sources” section describes the
various initiation scenarios considered. The section
titled “Cause Determination” describes the specific
cause of this accident. The section “Evaluation of
Thermal Stability” describes the information that exist-
ed prior to the event to determine if the process
developers had sufficient warning of the potential for
this accident. “Lessons Learned illustrates what signif-
icant lessons should be taken from this accident, and
the final section, “Recommendations for Inherently
Safer Design,” lists some possible redesign considera-
tions that would limit the potential for a similar acci-
dent to reoccur.
BACKGROUND
Product Description
The chemical mixture that underwent the unde-
sired chemical reaction was a powder consisting of
five different materials: sodium dichloroisocyanurate
(NaDCC, an oxidizer, approximately 60% by weight),
June 2003 75
Figure 1. Block flow diagram showing the production process.
two inert chemicals (10% by weight), and two organic
chemicals (30% by weight). All five of the powders are
white in color and have similar particle size distribu-
tions. The chemical mixture is packaged for sale as a
consumer product.
Process Description
The processes involved in the production of this
product can be divided into three steps: filling, mixing,
and packaging. The automated filling station is located
in a room adjacent to the production room. The envi-
ronments for both the filling room and the blending
room are carefully maintained at approximately 14" C
and 2% relative humidity. Figure 1 illustrates the
process.
FWg
The NaDCC and two other ingredients are added to
the blender automatically. This is done by filling a
hopper with material and allowing it to empty into a
drag conveyor for a predetermined amount of time.
The drag conveyor operates by pulling the material
through a pipe using ultra-high molecular weight
(UHMW) polyethylene pucks. The conveyor charges
the material into one of two ribbon blenders. In order
to prevent material from backing up into the filling
tube below the drag conveyer, the ribbon blender is
jogged forward every several minutes. After the first
three ingredients are added, the remaining two ingre-
dients are added by hand into the top of the blender.
The total weight of material added to the blender is
500 kilograms.
-g
After all five materials have been added to the
blender, the mixing process is begun. The ribbon
blender is run for 15 minutes. A ribbon blender works
by rotating a helical blade through a trough filled with
the material to be mixed. The ribbon consists of two
counter-acting blades mounted onto a central shaft.
One of the blades acts to move material slowly in one
direction, while the other acts to move material quick-
ly in the opposite direction. Mixing is accomplished
through the shearing motion induced by the counter-
acting blades. After the 15-minute mixing time, a sam-
ple of the material is taken for quality control. If the
sample passes the analysis, the material is sent for
packaging.
76 June 2003
packaging
The material drops from a hole in the center of the
blender, through two knife gates, a diverter leg, and into
a second drag conveyer. The diverter leg is used to
obtain the quality control sample. A level indicator is
positioned several inches above the drag conveyor.
When the level indicator is satisfied, indicating that the
level of material is equal to the height of the indicator,
the upper gate valve closes. When the level indicator is
not satisfied, the upper gate valve remains open allow-
ing material to flow down to the drag conveyor. The
material is pulled through a pipe and deposited into a
hopper. The material is emptied from this hopper into
two separate hoppers, labeled A and B. Hoppers A and
B both contain a level indicator, which acts to control
which of the two hoppers is filled from the hopper locat-
ed above. The material is emptied from Hoppers A and
B into blister packs formed and sealed in a machine
designed for this purpose.
Accident Summary
The following chronology of the accident was pre-
pared from witness interviews. All times are approxi-
mate. At 830 a.m. two operators began filling Blender
A with raw materials. The filling was completed, and
the material was mixed for 15 minutes. At 930 a.m., a
quality control sample was pulled from Blender A, and
filling commenced for Blender B. At 1O:OO a.m., a QC
sample was pulled from Blender B, and the contents
of Blender A were sent to the packaging machine.
Operators took a lunch break at 12:15 p.m., and
returned at 12:50 p.m. At that time, no changes were
observed in the material or the environment. At 1:00
p.m., the contents of Blender B were sent to the pack-
aging machine. Approximately three minutes into the
packaging process, the following events were
observed:
Dust emission from the sampling port
White powder spraying from gaskets
Hatch and dust collectors shaking
White smoke from the blender filling the upper
portion of room
Greenish smoke traveling toward the floors
The building was evacuated at 1:15 p.m. The sprin-
kler system, which had activated during the evacua-
tion, was shut off at 130 p.m.
Process Safety Progress 6'01.22, No.2)
INVESTIGATION
The scientific method was used to investigate the
cause and mechanisms of this accident. The scientific
method consists of defining the problem, gathering
available data (evidence), analyzing the data, develop-
ing hypotheses, testing the hypotheses, and finally
selecting the hypothesis that best fits the data and
analysis.
This accident was the result of an undesired chemi-
cal reaction. During the preliminary investigation, two
hypotheses were developed that could potentially
explain the accident-hydrolysis and thermal decom-
position. Once the specific reaction mechanism was
determined, additional hypotheses were formed to
determine what initiated the reaction.
To evaluate these hypotheses, investigators
reviewed the chemical hazard literature, performed a
detailed examination of the equipment, interviewed
witnesses, performed numerous tests, and analyzed
all of the available data.
Review of Chemical Hazard Literature
The available chemical literature was reviewed to
better understand the hazards associated with the
materials used in the formulation of this product. A
variety of information sources were consulted
including:
Manufacturers’ material safety data sheets (MSDS)
for each component
Technical Product Information bulletin for NaDCC
Hawley’s Condensed Chemical Dictionary [31
Brethem’ck’s Handbook of Reactive Chemical Haz-
ards [41
The primary component in the product is NaDCC.
NFPA classifies NaDCC as a solid oxidizer with a
reactivity rating of 2, a material that is normally
unstable and readily undergoes violent chemical
change at elevated temperatures and pressures but
does not detonate. The literature points to several
hazards associated with the handling of NaDCC. It is
known to undergo complete thermal decomposi-
tion, liberating a dense white smoke that contains
chlorine gas. NaDCC is reported to be incompatible
with the following chemicals:
0 Acids
0 Alcohols
0 Aliphatic and aromatic compounds
0 Amines
0 Ammonia and ammonium salts
0 Bases
0 Floor sweeping compounds
0 Glycerin, paint, oils, and greases
0 Moisture
0 Peroxides
0 Phenols
0 Petroleum products
0 Reducing agents
0 Solvents
This does not remesent a comdete list of all mate-
rials incompatiblg with NaDCk. It is known that
NaDCC can ignite some organic materials on contact.
Process Safety Progress (V01.22, No.2)
The technical literature stresses the need to keep
NaDCC isolated from other materials, and from heat
or flame. The presence of NaDCC and similar chemi-
cals in commercial fires has been determined to great-
ly increase heat release rates and toxicity of the fire
gases [51. Based on the literature review, it was con-
cluded that the product formulation could undergo a
thermal decomposition.
Theoretical Considerations of Reactivity Hazards
Simple theoretical considerations were employed
to determine the potential degree of reactivity hazard
of the product formulation. A useful tool for this pur-
pose is the CHETAH computer code [61. The CHETAH
code, developed by the American Society for Testing
and Materials (ASTM) for its subcommittee E27.07,
was used to evaluate the thermal decomposition risk
associated with the NaDCC molecule. In the CHETAH
program, properties of individual molecules can be
evaluated using the Benson group contribution
method. The CHETAH code estimated the risk of haz-
ard associated with this chemical as medium or high,
depending on the specific values used in the group
contribution method.
However, NaDCC does not lend itself readily to
analysis using the CHETAH code due to the presence
of chlorine atoms which are not accounted for in the
Benson method. A greatly simplified application of
the CHETAH criteria was employed. The first consid-
eration was the oxygen balance of the mixture.
Neglecting the presence of sodium and chlorine, the
oxygen balance for the mixture was calculated to be
-56%.This is within the high reactivity hazard range
of -120%to +80%. The enthalpy of thermal decom-
position was estimated as nearly -1,000 cal/g, also
indicating a high reactivity hazard potential.
Although these results are approximate, they indi-
cate that, like NaDCC, the product formulation pres-
ents a high potential as a reactivity hazard.
Examination of Artikts
The physical equipment and surrounding area
were carefully examined for any physical signs indi-
cating the cause of the accident, as well as to charac-
terize the extent of the damage. Many of the system
components were removed for more detailed labora-
tory examination.
Figure 2 depicts how the blender and conveyor
systems were configured, and identifies several of the
examined components. All of the equipment and con-
veyors filled with the mixture were found to have var-
ious amounts of thermal damage. The components
were filled with a black, porous material, similar to
ash or char, which had a strong chlorine odor.
The cover panels for the blender had been blown
o p e n during the accident, a n d portions of the
blender contents were ejected. This ejected material
caused thermal damage to the surfaces on which it
landed. With the exception of thermal damage
caused by this ejected material, n o other objects
exhibited signs of external heating. N o signs of elec-
June 2003 77
Table 1. Differential scanning calorimetry data.
- __ ~_ _ .._ _ __ _- _-. __ -- -
._ __.- --
Material ____ - . _ Event ~___- - _ _ _ - ____ _ _
100% NaDCC 1. Endotherm at 97" C
-~~~
__-._____ - - 2. anificant Exotherm-~ at 240"____
~
to 260" C (literature)
_ _ _ _ _50%
50% NaDCC, _ _ _ _Inert
_ _ _ - _
Endotherm
_____. - _ _at
_ 88" C _ ~_- - -
50% NaDCC, 50% Fuel 1. Endotherm at 66" C
2. Significant Exotherm at 142" C

trical or mechanical failures were observed on any

of the components. All of the observed damage was
consistent with exposure to an exothermic chemical
reaction.
Ribbon
Chemical Samples Blender
Seventy-four chemical samples were collected dur-
ing inspections at the facility. These samples included Upper Knife Gate
various examples of the product from the previous
batches, samples of the five raw ingredients, and vari-
ous samples of reacted material collected throughout
r Knife Gdte
the system. The majority of the samples collected of
reacted material had a similar appearance: dark
brown to black in color, porous, and charred.
Valve
TESTING
Throughout the course of this investigation, a num-
ber of tests were performed to describe the character-
istics of the chemicals and to address the specific
hypotheses regarding the mode of failure. The results Spool Piece with
of these tests are presented below. Level Indicator

Propagation Testing (Hot Wire Initiation)

The purpose of this test was to establish the feasi-
bility of the thermal decomposition of the product for- Conveyor
mulation. In these propagation tests, a quantity of the
product was placed in contact with a heated wire for Figure 2. Diagram of blender and conveyor assembly.
five seconds. This was enough to initiate a self-sus-
taining thermal decomposition reaction. A linear
with a propane torch flame, sufficient time to initiate a
propagation rate of 0.1 to 0.2 cm/s was measured. A self-sustaining thermal decomposition reaction in
temperature of 150" C was recorded in the bulk mate-
each sample. In both tests, the sample remained virtu-
rial in the vicinity of the reacting front. The reaction
ally unchanged for several seconds after the heat
liberated a dense white smoke, with a loss of approxi-
source was removed and before the reaction was
mately 50% of the initial mass. The volume of the
observable. The reaction produced a dense white
material remained approximately the same. The reac-
smoke and a color change in both samples. In addi-
tion product had the consistency of "fire brick" with
tion, both samples ejected material out of the jar, and
colored striations of white, light brown, dark brown,
exhibited a significant decrease in density. The reac-
and yellow. A similar test was undertaken using 100%
tion product in the production sample had a dark
NaDCC. The linear propagation rate was measured to
brown, charred appearance, similar to the material
be approximately .06 to 0.1 cm/s. The product of this
observed at the accident scene. The NaDCC sample
test had the appearance of a uniform yellow/orange
had a texture similar to the subject material. However,
color similar to "fire brick."
this reaction product was yellow and light orange in
color, as opposed to the dark brown color of the reac-
Propagation Testing (Flame Impingement on tion product of the production sample. A thermocou-
ContainerWall) ple was placed in the center of each sample to record
The purpose of this test was to simulate, albeit changes in the bulk temperature as the reaction pro-
crudely, the formation of a hotspot. In these propaga- ceeded. The highest recorded temperature in the pro-
tion tests one small glass jar was filled with approxi- duction sample test was approximately 450" C. The
mately 100 grams of the production mixture, and highest temperature in the NaDCC test was GOO0 c.
another was prepared with 100 grams of NaDCC. The
exterior of each jar was contacted for five seconds

78 June 2003 Process Safety Progress 0'01.22, N0.2)

Thermal Analysis
To investigate some possible effects of component
and/or particle segregation, different compositions of
material were prepared and examined using differen-
tial scanning calorimetry (DSC). These material sam-
ples were analyzed for thermal activity between the
temperatures of 25" C and 150" C. The DSC data is
summarized in Table 1.
Accelerated rate calorimetry (ARC) testing was per-
formed to gain more insight into the thermal stability
of the product material and various other composi-
tions of the ingredients. The results of the ARC testing
indicated a typical onset temperature of approximate-
ly 90" C, and a temperature at maximum rate of 150"
to 200" c.
Moisture Testing
The possibility of initiating a thermal decomposi-
tion reaction by first initiating a hydrolysis reaction
was tested by adding a 4 ml aliquot of water to 30
grams of the production mixture. Adding water
caused a momentary temperature rise up to 115" C.
Several tests were conducted with various amounts of
water and the product mixture, but all failed to initiate
a thermal decomposition. The reacted material had
the visual appearance of a white solid mass, very simi-
lar to the starting material.
Contaminant Testing
The possibility that the reaction initiated from
exposure to a contaminant was investigated by a sim-
ple screening test that consisted of adding a contami-
nant to a 100-gram sample of the mixture. Potential
contaminants were identified from inspections of the
accident scene. The contaminants tested in this analy-
sis included: organic grease, paper, oil, polyethylene
bag liner, and methanol. At no time during the 24-
hour duration of the test did any of the samples show
signs of temperature rise, self-heating, or thermal
decomposition.
Thermal Decomposition Was Undesired Reacdon
As stated previously, the scope of this investigation
was to determine why this accident occurred. Once
the specific cause of the accident is determined, it is
then possible to address safety concerns and possible
design changes to make the process inherently safer.
Observations made during the investigation suggested
two possible hypotheses for this accident: hydrolysis
and thermal decomposition. These hypotheses were
evaluated and compared to the physical evidence, test
data, and literature to determine which was the most
likely.
The hydrolysis reaction is initiated by the addition of
water to the mixture. The reaction is characterized by a
release of carbon dioxide and the formation of a white
residue. It is an exothermic reaction, but is not self-sus-
tainable. The thermal decomposition of the material is
characterized by the release of chlorine gas and the for-
mation of a yellow to dark brown porous inert residue.
This reaction is highly exothermic and self-sustaining. It
Process Safety Progress (Vol.22, No.2)
liberates enough heat to sustain a reaction after the ini-
tial heat source has been removed.
Damage to the equipment and the evidence of the
dark brown residue suggested that the reaction respon-
sible for the incident was the thermal decomposition
reaction. Corrosion of metal surfaces exposed to the
reaction products suggested that chlorine was evolved,
as opposed to carbon dioxide. While chlorine is itself
inert, it would rapidly form hydrochloric acid after com-
bining with water from the activated sprinkler head.
Physical evidence and testing supported thermal
decomposition, and refuted hydrolysis as the undesired
reaction that caused the accident.
ANALYSIS OF POTENTIAL INITIATION SOURCES
The next task was to determine how the thermal
decomposition was initiated. The following potential
initiation sources were considered:
Contamination
Hot surfaces
Electrical arc discharges
Hydrolysis
Misuse of smoking materials
Bulk heating due to friction
Hotspots due to friction
Self-heating
These potential initiation sources are each dis-
cussed below.
Contamination
The possibility of a contaminant being the cause of
the incident was carefully evaluated during this inves-
tigation. The following list of possible contaminants
was generated during the investigation:
Metal shavings
Alcohol
Paper
Polyethylene bag liner
Grease
Cutting fluid
Ink jet solvent
Trichloroisocyanuric acid
Contaminants in the raw ingredients
No evidence of contamination could be found that
would have initiated the reaction by direct contact.
Initiation by contamination was tested for a sample of
the likely material and found not to occur. Of the
materials that could have reasonably contaminated the
mixture, none are capable of self-heating. If a contam-
inant was present, it could possibly have acted to
lower the initiation temperature of the thermal
decomposition reaction, but not necessarily initiate
the reaction on its own.
Hot Surfaces
The potential for an external equipment malfunc-
tion causing a hot surface was examined during the
investigation. The two closest pieces of equipment to
the chemicals were a level indicator and the drive
motor. The level indicator located in the spool piece
below the blender showed signs of thermal damage.
June 2003 79
An inspection of the level indicator revealed that the
damage was a result of external heating as opposed to
an internal failure. The level indicator was a witness
to the heat evolved, and not the initiation source.
The investigation found that the drive motor was
drawing more electrical current than it had been
sized for. This could result in overheating of the rib-
bon drive motors. However, given the location of the
motor in relationship to the blender, and the short
time interval in which the motor operated, it would be
an unlikely initiation source. The metal used in the
housing of the motor, as well as the shaft that drives
the ribbon, would act as a sufficient heat sink such
that the temperature inside the blender would be neg-
ligibly affected by the motor.
Electrical Discharge
The possibility of static discharge was considered as
a possible initiation source. The equipment was suffi-
ciently grounded, so the likelihood of a static discharge
was low. However, one of the gaskets in the lower drag
conveyor was missing the bonding strip that grounds
the equipment. The possibility of initiation was tested
by the use of a high-voltage Tesla coil to generate an
electrical arc into a sample of material. This test failed to
initiate the thermal decomposition reaction.
The knife gates were examined to determine if
their operation had been producing sparks. N o evi-
dence of abrasive contact was observed on the
exposed surfaces of the knife gates. This would indi-
cate that they were operating without producing any
sparks. However, the electrical arc test refuted the
likelihood that, had the gates been sparking, they
would have been an adequate initiation source.
Hydrolysis
The possibility that the thermal decomposition was
initiated by the addition of water was also examined.
During the hydrolysis reaction, some heat is generat-
ed. It was hypothesized that water could have entered
the blender and initiated a localized hydrolysis reac-
tion that could have subsequently initiated the thermal
decomposition. However, no viable pathway could be
found for water to enter the batch, and the testing
performed to evaluate this hypothesis was unsuccess-
ful in initiating a thermal decomposition. For these
reasons, it was concluded that hydrolysis was not the
initiating event.
Misuse of Smoking Materials
Other possible initiation surfaces were considered,
such as small flames or glowing coals from smoking
material. However, no evidence was found indicating
that a foreign object, such as smoking material, had
contacted the material and acted as the initiation source.
Bulk Heating due to Friction
Frictional heating from two sources was consid-
ered: the drag conveyor and the ribbon blender.
Pulling the material through the drag conveyor was
considered as a possible initiation source. Some fric-
80 June 2003
tion would be generated as a result of this method of
conveying material. However, the transient nature of a
conveyor system would make initiation difficult. Much
of the heat generated in the drag conveyor would be
dissipated into the pipe walls. While heating is possi-
ble in the drag conveyor, the conditions do not exist
such that initiation is a strong possibility.
Friction incurred in mixing the material in the rib-
bon blender was also considered. It is known that
mixing solid crystals in a ribbon blender will result in
frictional heating, and in one of the quality control
batches the temperature of the bulk material was
higher than expected. The material would act as a
very good insulator for heat, such that the conditions
in the blender were nearly adiabatic, allowing any
heat generated to build up, as opposed to dissipating
into the surrounding material. However, a simple
energy balance on the ribbon blender predicted a
temperature rise of less than l o C for the mixing
process. Therefore, bulk heating due to friction was
not considered to be the initiation source.
Hotspots due to Friction
Friction in the blender can also cause the formation
of hotspots within the mixture in localized areas due
to the shearing action of the blender. These hotspots
can be hotter than the bulk temperature of the mix-
ture. Extended duration mixing will tend to homoge-
nize the mixture, thereby making the detection of
localized hotspots difficult. The hypothesis that
hotspots formed by friction in the ribbon blender was
retained for further consideration.
EVALUATION OF THERMAL STABlLllY
The self-heating potential of the product was evalu-
ated by estimating the kinetic parameters from the
ARC data [7-91. Since the thermal decomposition
occurred approximately three hours after mixing, the
criterion used to evaluate thermal stability was the
bulk temperature required to achieve a thermal run-
away within three hours. The results indicated that
this would require a bulk temperature of approxi-
mately 75" C, compared to the room temperature of
1 4 O C. Thus, initiation by self-heating was refuted.
The only initiation hypothesis remaining was initia-
tion by hotspots during mixing. Additional support for
this explanation was found during the investigation
when it was learned that a noticeable temperature rise
was observed by operators preparing 50-kilogram pilot-
scale batches. Specifically, an operator commented to
his supervisor that the batch was uncomfortably warm
to the touch. Coupled with the ARC data and hazard lit-
erature, this observation was significant.
CAUSE DETERMINATION
The goal of an accident investigation is to deter-
mine the factors that led to the event. An accident
such as this one is typically a result of several factors:
human, mechanical, and environmental. Multiple
causes were considered during the course of this
investigation. It is clear that the incident was the result
of a runaway thermal decomposition of the product.
Process Safety Progress (V01.22, No.2)
 N o evidence has been found that operator error con-
tributed to the event. There appears to have been no
deviation from the operation protocols for the produc-
tion of the mixture. In addition, no evidence of mechan-
ical malfunction has been found to contribute to the
event. The environment was carefully maintained and
did not vary prior to the incident. With the elimination
of the typical cause-and-effect scenarios that cause acci-
dents, it becomes necessary to look at problems inher-
ent in the design and operation of the system.
The literature review, the testing, and the engineer-
ing analysis of the data point to the ribbon blender as
the origin of the event. The physical evidence also
supports this conclusion. Had the reaction initiated in
the equipment below the blender, the increase in vol-
ume of the residue would have sealed off the drag
conveyor pipe so no material could have been blown
upstream. Material was found to have been forced as
far as six feet upstream in the drag conveyor. Also, the
reaction would have had difficulty traveling up into
the ribbon blender against the flow of material, and
through the two knife gates, which were closed soon
after the reaction manifested itself.
The ultimate cause of this accident was most likely
the frictional heating of the batch that resulted in a
thermal runaway. The most probable scenario is that a
localized hotspot formed within the batch of product.
The decomposition incubated for approximately three
hours before the runaway (uncontrolled exotherm)
occurred. The ability of the product to support a ther-
mal runaway is an inherent characteristic of the mate-
rial. In order to initiate the thermal decomposition at
low ambient temperature, the material must be sub-
jected to an initiation (energy) source.
The ease of initiation depends in large part on the
amount of material. Small quantities of material lose
heat quickly and therefore have larger initiation ener-
gy requirements. Large quantities of material tend to
trap heat, and therefore have smaller initiation energy
requirements. The large size of the production batch
made it susceptible to low-energy initiation sources,
such as friction.
LESSONS LEARNED
The investigation concluded that the accident was
caused by an inherent problem in the design of the
process. A thermally unstable material was mixed in
large quantity in equipment that imparts significant
frictional heating during mixing. N o mechanical or
chemical defects or operator error could be identified
as contributing to this accident.
A review of all the information available, both before
and after the accident occurred, reveal that this accident
could have been prevented. Taken separately, the
observations from the literature, the ARC data, and the
previous scale-up experience indicate that care should
be taken in handling this material. It is only after these
three separate observations are combined that the true
degree of hazard becomes apparent.
During the development of this product, the
researchers did not impart their experiences with the
Process Safety Progress (V01.22, No.2)
ARC data or the chemical literature to the engineering
staff designing the process. Further, the engineering staff
did not communicate the temperature rise observed
during early mixing studies to the research staff. It was
not until after the accident that both parties had the
benefit of all the pre-accident observations.
Two significant lessons can be learned from this
accident. The ARC testing, which was performed two
years prior to the accident, was never carefully ana-
lyzed. Had a knowledgeable member of the research
staff studied the ARC data, it is likely that the degree
of hazard would have been more accurately assessed.
Unfortunately the ARC data was never carefully
reviewed, and coupled with the experience of safely
working with bench-scale batches, the material was
assumed to be safe.
Another significant lesson to be learned from this
accident is that open communication between the
research and engineering staffs might have prevent-
ed this accident. Had these observations all been
openly communicated between the two groups, sim-
ple equipment design changes could have been
made that would have prevented this accident.
RECOMMENDATIONSFOR INHERENTLY SAFER DESIGN
While the NaDCC mixture does represent a hazard,
it could be safely handled if precautions are taken in
the design. Two separate approaches can be taken in
this application to significantly reduce the likelihood
of a similar event. The process can be made inherent-
ly safer if the size of the batches is reduced, and the
amount of heat added to the process is minimized
[lo]. The following list contains several suggested
methods of reducing the inherent risk associated with
this process.
Mix the inert ingredients separately and meter in
the NaDCC.
Use a different type of blender that will not impart
as much friction to the system.
Evaluate the possibility of modlfying the order and
method of addition to the blender.
Consider a different type of conveyor system to
eliminate or reduce the heat produced in the con-
veying of the material.
Modify the formula to reduce the instability inher-
ent in the current formulation.
Limit the amount of material processed such that
the minimum thickness is below the critical half-
thickness.
Limit the amount of time the material sits before
packaging.
Incorporate a cooling system into the process.
Add the ingredients directly into the packages
without mixing.
The above list offers some general issues to consider.
It is likely that a combination of some of the above sug-
gestions will make for a safer process.
CONCLUSIONS
This accident investigation described a toxic gas
release caused by the thermal decomposition of a
June2003 81
bulk powder blend containing NaDCC. The accident
occurred during the fourth batch of the first produc-
tion campaign. The 500-kilogram batch was being
mixed in a ribbon blender. It was determined that the
thermal decomposition was initiated by frictional
heating during the mixing operation.
A n important lesson learned from this accident is the
importance of communication and understanding of
process safety information. Three different people with-
in the manufacturer’s organization had specific evidence
for the hazard of this NaDCC mixture from chemical
hazard literature, ARC data, and the pilot-scale observa-
tions of self-heating during the mixing. Considered sep-
arately, each of these types of evidence indicated a
reactive material hazard. Considered together, this evi-
dence indicated a highprobability of a reactive materi-
als accident.
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82 June 2003
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