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PLANT SAFETY AND ENVIRONMENT SPECIALREPORT

Water among causes for


storage tank explosion
Reinvestigation uncovers true accident events
M. FERJENCIK and B. JANOVSKY, University of Pardubice, Pardubice, Czech Republic

A
n explosion occurred inside a bitu- vertical cylinder with a fixed roof. It was ing was to be used only when the bitumen
men storage tank. An abrupt inter- standing in a concrete emergency sump. The temperature inside the tank was higher
ruption of the purging steam dis- tank communicated with the surrounding than 190°C. More than one day before the
charge from the tank preceded the accident. air via a couple of vents which were placed accident, the bitumen level was 65 cm and
The suspected ignition sources alone would at the southern edge of its roof. The total at 155°C. These parameters were kept for
not be able to cause the observed explo- tank volume was 1,200 m3—height 10 m, more than 24 hr. Conditions inside the
sion. An additional impulse must have been diameter 12.4 m (Fig. 1). tank started to change again approximately
present. Careful analysis of the event led to The tank was equipped with openings 3 hrs 40 minutes before the accident.
the conclusion that the explosion was prob- and pipe connections. One hatch and seven At that time, 120 ton batch of bitumen
ably preceded by water that was introduced pipe connections were in the bottom part of was transported into the storage tank. Since
inside the tank. Iron sulfides were present its wall. There were two connections of the the temperature of the influent bitumen was
under the tank roof and combined with steam heating system that kept the bitumen higher than 200°C (up to 250°C), steam
the injection of water (causing the fresh air inside the tank hot and liquid. The second purging was commenced. The transport
suction and atmosphere movement inside hatch and seven other openings were in was finished 40 min before the accident—
the tank) and this explained the explosion the roof of the tank, and one blind nozzle the bitumen level was 180 cm and at 205°C.
under actual conditions. was in the upper part of the tank wall. Fig. Steam heating and steam purging were left
2 only shows the roof openings that were in operation; steam pressure was about 4.5
Introduction. Trevor Kletz wrote an considered to play a role in the accident. bar and temperature about 140°C. The fill-
anecdote in which he exaggerated the dan- The steam inlet (50-mm diameter) was ing pipeline was emptied into the storage
gerous properties of water.1 Nevertheless, located close to two vent nozzles (200-mm tank by pressurized air. All manipulations
he still described water as an extinguish- diameter each). A steam pipe with a 25-mm connected with the transport were finished
ing agent. However, in the accident that diameter was inserted into the steam inlet. 25 min before the accident.
occurred, a situation encountered showed Its end piece inside the tank was used for About 25 min later, an explosion
that water played the opposite role. Even steam purging. It was less than 1.5-m long; occurred inside the bitumen storage, blow-
introducing a relatively small amount of its mouth was blind and its wall was perfo- ing off the tank roof. After the explosion,
water into a large bitumen tank seems to rated. The bitumen circulation inlet pipe the tank contents started to burn. The roof
have triggered the accident that resulted in nozzle (125-mm diameter) position was fell beside the emergency sump and leaned
an explosion and a fire. across the roof at the northwest edge. The against the southwest wall. The explosion
This article will present the accident’s bitumen circulation inlet—a carbon steel did not damage the tank wall, but a subse-
reinvestigation. It is based on a report pipe, 100-mm diameter was inserted—was quent fire destroyed the south-southwestern
that was prepared by a plant investigation the newest tank opening. It was welded dur- part. A layer of coke sediments were prob-
committee. However, the original report ing a scheduled outage of the tank, roughly
ignored the necessity to explain an abrupt six weeks before the accident. The second
interruption of purging steam discharge most recent opening was two years old.
from the tank which preceded the accident.
The reinvestigation concentrates on this Chronological order. Operational
event and makes it the focal point to shed records showed that during the last four
light on why the accident occurred. days before the accident, the bitumen level
inside the storage tank was relatively low
Installation. The accident occurred more (maximum 330 cm) and the temperature
than five years ago in a plant that processed was between 150°C–155°C. Steam heat-
heavy-oil hydrocarbons. The event involved ing was operated permanently and steam
an almost 40-yr-old bitumen storage tank. purging was inactive. It was in accordance FIG. 1 Bitumen storage tank, front view.
The tank was an insulated, carbon-steel, with operational instructions: steam purg-
HYDROCARBON PROCESSING NOVEMBER 2010
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SPECIALREPORT PLANT SAFETY AND ENVIRONMENT

ably burned at relatively high temperatures. Oxidant. For at least four days before the able liquid containing light hydrocarbons
The fire was localized and extinguished in accident, steam purging had been inactive would then have been transported into the
less than 5 hr. It did not cause material dam- on the tank. Its gaseous volume commu- bitumen storage tank as soon as any of the
age outside the bitumen storage tank nor nicated freely with the atmosphere outside pipelines connected to the manifold would
any fatalities or injuries. Unburned bitumen vent openings. Tank space above the liquid have been emptied into it. Other potential
had to be placed in barrels and reprocessed. level undoubtedly contained mainly air sources of fuel such as catalytic cracking on
No anomalies were found in the unburned at the start of steam purging 3 hr 40 min steam heating pipes or steam reforming are
liquid during its removal and reprocessing. before the accident. Sweep steam purging not considered to be probable since tempera-
was used to make the atmosphere of the tures inside the tank were not high enough.
Additional observations. The south- tank inert, but it was not able to perfectly Observed explosion outcomes enabled
ern part of the tank roof, with vent nozzles, mix the whole gaseous volume when the estimating the amount of light hydrocar-
was within the scope of one camera belong- liquid level was low.2 Steam is much lighter bons that had to be present in a flammable
ing to the plant security system. Relevant than air (and hydrocarbon vapors). The cloud inside the tank. The light hydrocar-
record analysis provided interesting addi- arrangement of the steam inlet pipe did not bons originated from lacquer diluents, the
tional information about what happened make the steam move into the lower parts boiling interval was 135°C–220°C, LFL
a few minutes before the accident. Records of the tank. Only the upper part of the tank is 0.8% vol. and upper flammable level
confirmed that emptying the filling line was (about 20% of its total volume, according (UFL) is 6.5% vol. To assess the minimum
performed within a 15-min time period, to an estimation made by plant personnel) amount of light hydrocarbons necessary to
ending 25 min before the accident—per- is believed to have been filled with a steam have lifted the tank roof off, it was neces-
formed in accordance with operational blanket. Lower parts of the gaseous volume sary to start with the overpressure, which
instructions. Records showed that a per- probably still contained mainly air during could have caused it. Overpressure at 12
manent and stable steam discharge from the explosion. kPa is enough pressure to lift a storage
tank vents occurred 3 hr 40 min before the Large volumes of bitumen in the storage tank roof off.3
accident and finished abruptly 47 s before tank were used from time to time as ter- The question is, how large does the
the explosion. During the last 47 s, no minal volume to empty various connected flammable cloud have to be if it is capable
outflows from vents were visible. Also, the pipes by air. These emptying operations of generating 12 kPa of overpressure inside
course of the explosion was recorded. The brought additional oxidant into the tank. the tank? From the state equation, it fol-
lifting of the roof was visible, followed by lows that if the vapor space volume inside
a rising fireball and flames. Evidently, the Fuel. Flammable, gaseous substances had the tank is 989 m 3, then an increase in
tank roof was blown off by the explosion to be present in the atmosphere inside the the vapor volume should be equal to 117
of a flammable mixture in the tank atmo- tank in a concentration above the lower m3 under normal pressure. This volume
sphere. The investigations after the accident flammability limit for the explosion to increase is caused by generating hot com-
showed that the vents were free and that the occur. The bitumen itself releases a certain bustion products. The number of moles
steam pipeline to the steam-purging inlet amount of light hydrocarbons, but mea- inside the tank should not change during
was open and free, too. surements indicate that the total content combustion. Only the temperature differ-
above the bitumen level is one order below ence between the initial and final states
Searching for accident causes. The any conceivable lower flammable limit could cause the volume increase. The sys-
fire triangle describes three requirements (LFL). The bitumen present inside the tank tem’s initial temperature was supposed to
that have to be fulfilled for a fire/explo- before the accident was of standard quality; be equal to 478 K. The combustion prod-
sion of a gas mixture: an oxidant, a fuel and therefore, the fuel source for the explosion ucts’ temperature was estimated to be 1,500
an ignition source.2 Accident causes com- had to be found elsewhere. K. This temperature is in accordance that
bine the three requirements. Identifying The filling pipeline came into the tank the flame temperature at the LFL for meth-
the direct accident cause was not possible from a manifold to which pipelines from ane is 1,498 K and approximately 1,573 K
without identifying the specific oxidant, a few other storage tanks were also con- for other lower paraffinic hydrocarbons.4
fuel and ignition source that were present nected. Analyzing operational records Comparing these final and initial states,
inside the bitumen storage tank. showed that asphalt varnish was pumped an expansion factor equal to 3.14 was
through a pipeline that was connected to obtained. The equation for the volume of
Steam inlet Bitumen the manifold, more than two days before the explosive mixture capable of producing
pipe circulation the accident. The asphalt varnish repre- the given pressure increase is:
Vent inlet pipe
sented a mixture of bitumen (identical
nozzles Vexpl + 117 = Vexpl × 3.14.
with the stored one) and lacquer diluents.
If a check valve in the pipeline that was This results in 54.7 m3 of the explosive
used for pumping asphalt varnish had mixture, with a concentration equal to LFL.
not worked properly, a certain amount of The light hydrocarbons may be represented
varnish would have entered the manifold. by C9 fraction with a mean molecular
Insufficiently closing the check valve in its weight of 148.4 g/mol. Using the molecu-
closing direction is a rather frequent defect lar weight, the evaporated flammable vapor
S N
that cannot be excluded. amount is 1.66 kg. It is certainly the lowest
The liquid amount that would have possible amount, not taking into account
FIG. 2 Bitumen storage tank; an aerial entered the manifold in this case might the product cooling and venting through
view with selected openings. have easily reached many liters. Undesir- the two vent nozzles. Higher amounts of
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PLANT SAFETY AND ENVIRONMENT SPECIALREPORT

evaporated flammable vapors (e.g., 5 kg and pression and catalysts.5 Some alternatives cause a decrease in the auto-ignition tem-
10 kg) would lead to higher values of the may be excluded immediately. perature of flammable vapors and lead to
calculated overpressures (36.2 kPa and 72.4 There was no hot work carried out at ignition after an induction period.2 Without
kPa, respectively). Since these values are the tank weeks before the accident. A com- a catalyst, auto-ignition of lacquer diluent
well above the 12 kPa, neither cooling nor pression or decompression sharp enough to vapors is not possible under 240°C.
venting through two vent nozzles would ignite the flammable vapors is not conceiv- Pyrophoric iron sulfides form when iron
have prevented the roof from lifting off. able under conditions inside the tank. No is exposed to hydrogen sulfide (H2S), or any
Such an amount of flammable vapors could moving mechanical parts that would be other compound that contains sulfur, in an
have easily originated in the asphalt varnish able to cause friction or sparks were present oxygen-deficient atmosphere. Pyrophoric
that entered the tank via the manifold. The inside the tank. iron sulfide may form in heated bitumen
flammable cloud could have been formed Movement of nonconductive liquid into storage tanks as the result of a reaction
after the temperature increase during the the tank finished at least 25 min before the between H2S given off from the bitumen
inflow of hot bitumen between –3:40 and accident; hence collection and discharge of surface and iron in the form of rust on the
–0:40 hr. Hydrocarbon vapors are heavier static electricity are not considered to be tank roof.6 H2S was present inside the tank.
than air so the operation of sweep steam probable to ignite the explosion. Hot sur- Hence, the area of new bitumen circulation
purging would not have removed them faces, in the usual meaning of this term, inlet welds seemed to fulfill all conditions
from the tank with a low bitumen level. were not present inside the tank. However, for pyrophoric iron sulfide formation.
Fig. 3 illustrates the situation that is a layer of coke sediments were found on the
supposed to have been established inside south–southwestern wall, burning intensely Examining the facts and formu-
the tank after adding hot bitumen. after the explosion. Suspicion arose—the lating hypotheses. Three possible
coke sediments had been smoldering even ignition sources were identified: smol-
Possible ignition sources. Some igni- before the accident and they ignited the dering coke, auto-ignition catalysts and
tion sources may include hot work, static flammable cloud. The possible presence of pyrophoric iron sulfides. Examination of
electricity, hot surfaces, pyrophoric iron sul- catalysts (e.g., coke particles with large active these three hypotheses with known facts is
fides, pressure (compression ignition), fric- surfaces) in liquid bitumen was considered, necessary, and Table 1 represents the fact/
tion and mechanical sparks, sudden decom- too. The presence of catalytic surfaces could hypothesis matrix.7

TABLE 1. Fact/hypothesis matrix. Legend: (+) compatible with hypothesis; (×) not likely
Temperatures inside tank No anomalies (coke particles, Abrupt interruption of Tank roof fell beside
between 140°C and 205°C, hot spots) were found in steam discharge 47 sec tank in south–
Fact or condition/hypothesis steam blanket under roof unburned bitumen before the explosion southwest direction
Light hydrocarbon vapors + + × ×
ignited by smoldering coke
on south–southwest wall
Light hydrocarbon vapors + × × +
auto-ignited after
induction period
Light hydrocarbon vapors
ignited by pyrophoric iron
sulfides from new weld × + × +

Steam Steam
outlet inlet Air Injection
intake of water
Bitumen circulation inlet pipe

Steam blanket, 140°C


Position of
new weld
Shrinking
of steam
Air with hydrocarbon vapors and air
Fresh air
movement

Hydrocarbon vapors
raised by water
evaporation
Bitumen, 205°C

FIG. 3 Situation inside the tank, 30 min before the accident. FIG. 4 Situation inside the tank during water injection.

HYDROCARBON PROCESSING NOVEMBER 2010


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SPECIALREPORT PLANT SAFETY AND ENVIRONMENT

TABLE 2. Modified fact/hypothesis matrix. Legend: (+) compatible with hypothesis; (×) not likely
Temperatures inside tank No anomalies (coke particles, Abrupt interruption of steam Roof of the tank fell
between 140°C–205°C, hot spots) were found in discharge 47 s before beside tank in south to
Fact or condition/hypothesis steam blanket under roof unburned bitumen the explosion south-west direction
Light hydrocarbon vapors ignited + + + ×
by smoldering coke on south–
southwest wall after the
introduction of a small amount
of water
Auto-ignition of light hydrocarbon + × + +
vapors occurred after the
introduction of a small amount
of water
Light hydrocarbon vapors ignited + + + +
by pyrophoric iron sulfides from
new weld after introducing small
amounts of water

Penetration of piece at 4.5 bar. The injection would have


Welding of the Return of Bitumen level 120 t of bitumen
light hydro- abruptly cooled steam and gases inside the
bitumen bitumen tank 65 cm, Start of steam added, level
carbons into
circulation back into temperature purging raised to 180
pipe inlet— operation
bitumen
155°C— cm, temp. to
space, causing the gases to shrink. This
inside tank
approximately Approximately
Approximately
more than At -03:40 hr 205°C between results in under pressure inside the space,
6 weeks before 4 weeks before 1 day before -3:40 and -0:40 hr
2 days before reversing the flow through the vent nozzles.
The situation is illustrated in Fig. 4.
In Fig. 4, superheated water leaves
Emptying of Interruption of Penetration of
Spontaneous the holes in the end piece and some of it
Introduction of ignition of Explosion of air
pipe line, 10 m3 steam discharge fresh air to evaporates immediately (approximately
waste into pyrophoric and hydrocarbon
of air introduced pyrophoric iron
steam inlet pipe iron sulfides, vapors mixture 7.9%). Flash evaporation of water creates
inside the tank between sulfides at
release of
between -0:40 -00:00:47 and new weld an expanding zone around the end piece
at -00:00:47 sec sparks at 00:00:00 sec
and -0.25 hr 00:00:00 sec < 00:00:00
< 00:00:00 sec
inside. The temperature decreases to the
FIG. 5 Development of the accident. boiling point of water (100°C). The volume
of this zone is relatively small since one liter
of water creates 0.14 m3 of flash evaporated
Coke smoldering can develop slowly processes. It resulted from an additional steam. Tiny droplets of boiling water fly
and gradually, so there would have been no cause and probably contributed to the away from the expanding zone into much
reason for an abrupt interruption of steam ignition process. Closing or plugging the warmer steam and/or air around and below.
discharge. If the explosion was ignited by steam pipeline or the outage of the steam The droplets are heated and evaporated. The
smoldering coke at the south–southwestern supply system would have caused a slow tank atmosphere cools down and shrinks.
wall, then the final position of the blown decrease of steam discharge, not an abrupt Globally, 1.7 m3 of steam will emerge from
roof would have been expected on the interruption. An event must have occurred 1 L of water. Simple calculations show that,
opposite side of the tank. Catalyzed auto- that caused an immediate pressure decrease in evaporation and balancing temperatures
ignition would require the presence of a inside the gaseous volume of the tank. Such in 100 m3 of steam, the steam is cooled by
catalytic surface on the bitumen. However, an event could have been the steam pipeline 18.2°C and shrinks to 4.4 m3. Analogously,
no corresponding anomalies were indicated plugging with water. 100 m3 of air would be cooled by 24.8°C
in the liquid. Auto-ignition develops slowly Steam lines need to be equipped by and shrunk to 6.2 m3.
and gradually, thus giving no explanation steam traps. A steam trap is a device used to This process leads to a movement inside
for the abrupt interruption of steam dis- discharge condensate and non-condensable the tank atmosphere towards the expanding
charge. Pyrophoric iron sulfides spontane- gases while not permitting live steam escap- zone around the end piece of the steam-purg-
ously ignite after they dry out and come in ing. If the steam trap is not present or if it ing pipe. Possible evaporating droplets on the
contact with air, but there was no indica- fails, then a water plug may form inside the tank walls make this movement even stron-
tion that the steam blanket was replaced by pipeline. There are indications that a steam ger. If some droplets fell on bitumen liquid
air at new welds. Again, the abrupt inter- trap was not present in the lower part of the level, they would evaporate and raise hydro-
ruption of steam is not compatible with steam line to the steam purging inlet, so a carbon vapors above the liquid surface.
the hypothesis. water plug formation seemed possible. The mixture of water aerosol and cold
If one liter of water had penetrated into steam is relatively heavy and tends to sink
Water injection. None of the consid- the steam purging line it would have cre- into the air and hydrocarbon mixture.
ered ignition sources were able to explain ated a water plug about 2 m long. The plug Expansion in the steam-aerosol area and
satisfactorily the abrupt interruption of would have been transported into the end turbulences caused by water evaporation
steam discharge 47 sec before the explo- piece of the steam purging pipe. The water make the steam-aerosol area less permeable
sion. Evidently, the interruption did not would have been injected into the tank’s for downward flowing gas, especially in the
result in any of the conceivable ignition vapor space through tiny holes in the end vicinity of the end piece.
38
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PLANT SAFETY AND ENVIRONMENT

BORSIG
The estimations confirm that after water into the bitumen inside the tank; the cre-
injection, the overall balance of water evap- ation of pyrophoric iron sulfides at the new
oration (with a positive influence on pres- weld; and the introduction of water into
sure inside the tank) and steam/air shrink- the steam inlet pipe. The accident would
age (with a substantially higher negative never have occurred if a small amount of
influence on pressure inside the tank) will water had not been introduced into the
result in air intake through vent nozzles. steam purging inlet pipe. It is highly prob-
Cold and relatively heavy fresh air tends able that similar situations had occurred in
to sink through the steam pad into the air the tank’s 40-yr history, but the necessary
and to dilute the air and hydrocarbon mix- causes never coincided. Fig. 5 illustrates
ture. However, there was a zone consist- a probable multiple-root cause analysis,
ing of steam and aerosol that was denser which may lead to some lessons learned
than steam and obstructive due to turbu- from the accident while recommending
lences. This, combined with the sinking proper corrective measures. HP
and shrinking movements inside the zone,
would have caused part of the inflowing air LITERATURE CITED
1 Kletz, T. A., New Fire-fighting Agent Meets
to be sucked in a perpendicular direction
Opposition, By accident ... a life preventing them in
between the zone and the tank roof and industry, PFV Publications, London, 2000
to move along the roof into the peripheral 2 Crowl, D. A., “Understanding Explosions,”
parts of the tank (Fig. 4). Sinking fresh air American Institute of Chemical Engineers, New
and the steam pad at the southern wall may York, 2003.
3 Kletz, T. A., “Myths of the Chemical Industry,”
have also caused air movement at the oppo- The Institution of Chemical Engineers, Rugby,
site side upward against the wall. 1985.
4 Lees, F. P., Loss Prevention in the Process
Possible ignition sources after Industries, Second Edition, Butterworth-
water injection. Three new hypotheses Heinemann, Oxford, 1996.
5 IRP18 Committee, University of Calgary, Canada,
on possible ignition sources represent the http://www.firesandexplosions.ca/hazards/
interactions of sources that were selected ignition sources.php, September 24, 2007.
6 Davie, F. M., T. W. Nolan and S. Hoban, “Study
with water injection. The results of the
Leading examination are summarized in Table 2. of Iron Sulfide as a Possible Ignition Source in
the Storage of Heated Bitumen,” Journal of Loss
If the source were smoldering coke on the
Technology for south–southwest wall after the water injec-
7
Prevention in the Process Industry, Vol. 6, Issue 3,
pp. 139–143, September 1993.

Innovative tion, then the abrupt interruption of the


steam discharge is understandable. How-
Center for Chemical Process Safety, “Guidelines for
Investigating Chemical Process Incidents,”
American Institute of Chemical Engineers, New
Solutions ever, there is no new explanation of why
the tank roof fell in the opposite direction
York, 1992.

than would be expected. Similarly, for cata-


Pressure Vessels and lytic auto-ignition the presence of a cata-
Heat Exchangers lyst remains unexplained. The situation has Milos Ferjencik studied nuclear
engineering at Prague Technical Uni-
changed only for pyrophoric iron sulfides.
Reciprocating and versity and graduated in 1981. He
The preceding section explains that fresh air worked at Nuclear Research Institute,
Centrifugal Compressors could penetrate to a new weld after water and in various technical and research
for Process Gases
injection. Hence, conditions for sponta- positions. In 1991, Mr. Ferjencik concentrated on chemi-
cal risk analysis. In 1995 he started his own consultancy
Membrane Technology neous ignition of pyrophoric iron sulfides
profession. Mr. Ferjencik was an independent risk and
e.g. Emission Control Systems, would have been fulfilled. There is evidence reliability consultant and an external teacher at University
Vapour Recovery Units that such an ignition may produce sparks.6 of Pardubice. Most recently, Mr. Ferjencik has worked as
The immediate contact between the sulfide a full-time assistant professor of safety engineering at
Industrial Boilers and the University of Pardubice.
Power Plant Technology and the flammable mixture is not necessary.
Consequently, the pyrophoric iron sulfides
Industrial and Power Plant at the new weld might have acted as an igni-
Services Bretislav Janovsky received BS
tion source after introducing small amounts and PhD degrees from the University
of water into the steam inlet pipe. of Pardubice focusing on theory and
technology of explosives. He worked
Conclusions. The analysis helped com- in various technical and research posi-
BORSIG GROUP plete the time line of events leading to tions at the University of Pardubice and a privately held
company, TLP Prague. Dr. Janovsky concentrated on
Egellsstrasse 21 the accident (Fig. 5). Dashed borderlines consequence analysis under risk analysis in the process
D-13507 Berlin/Germany denote the events that cannot be proved. industries. He was a full-time assistant and associated
Phone: +49 (30) 4301-01
Fax: +49 (30) 4301-2236
Probably, the combination of four direct professor of safety engineering at the University of
Pardubice and started his own professional consultant
E-mail: info@borsig.de causes led to the accident: the inefficient business in 1995. Today, Dr. Janovsky is the research and
www.borsig.de sweep steam purging of the bitumen storage development director at OZM Research Bliznovice and
tank; the penetration of light hydrocarbons teaches part-time at the University of Pardubice.
Select 158 at www.HydrocarbonProcessing.com/RS

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