Bhopal Disaster

Bhopal 3/12/84

Release of toxic gases from a Chemical Plant

Worst Industrial Disaster in History

Up to 4,000 dead, 500,000 affected.

 Bhopal Disaster
ACCIDENT OVERVIEW
A pesticide plant in India produced the compound Methyl Iso Cyanate (MIC)
as an intermediate product in the process.
MIC is an extremely toxic and unstable substance and even in very small
quantities is fatal.
Large quantities of the MIC were stored in steel tank. The tank had many
safety features to maintain the product in a safe and stable form.
Economic pressures meant that most of these features were abandoned to save
money.
Water, inadvertently entered the storage tank and caused an exothermic,
runaway reaction to occur.
The MIC boiled up and MIC vapour was expelled through the bursting disc
vent.
The scrubber and flare stack were in-operational so the MIC vapour was
discharged directly to atmosphere.
The wind carried it as a plume over the adjacent city of Bhopal where the
victims were living.
 Bhopal Disaster
PLANT & PROCESS DESCRIPTION

The Union Carbide plant at Bhopal produced the product Sevin an

insecticide for spraying on crops.
The capacity of the plant was 5,000 tonnes of Sevin per annum. It
commenced full production in 1980.
The factory was located at the northern end of the town of Bhopal in what
was originally a relatively sparsely populated area.
Over the years though unplanned urban growth meant densely populated
suburbs were allowed to be built at the southern edge of the factory.

The prevailing wind was from the North.

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PLANT VIEW
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PLANT VIEW
Picture illustrates proximity of plant to residential urban neighbourhood.
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PLANT VIEW
Picture shows the plant as it is today.
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PROCESS DESCRIPTION
There were five main process areas on site:

Carbon Monoxide Production

Carbon plus Oxygen to Carbon Monoxide
Phosgene Manufacturing Plant
Carbon Monoxide plus Chlorine to Phosgene
Methyl Isocyanate Plant
Phosgene plus Methyl Amine to MIC
Alpha Napthol Plant
Sevin Plant
MIC plus Alpha Napthol to Sevin

MIC was produced by reacting Phosgene with Methyl Amine and

separating out the MIC by distillation. The liquid MIC was then pumped
to storage tanks.
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PROCESS DESCRIPTION
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PRODUCT DESCRIPTION
Although only MIC and Phosgene were implicated in the disaster, the
plant was characterized by the production and storage of a large number
of very dangerous compounds.
OH

Alpha Napthol

O H
O C N CH3
Sevin
1 - Naphthyl - N - Methyl - Carbamate
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PRODUCT DESCRIPTION
H
H
H C N Methyl Amine
H
H

Cl
O C Phosgene
Cl

H
H C O C N Methyl Iso Cyanate
H
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PRODUCT DESCRIPTION

Methyl Isocyanate (MIC) CH3NCO

Molecular Weight M = 57
Boiling Point at atmospheric pressure b.p. = 39 C
It is a colourless, highly volatile liquid at room temperatures with a
vapour twice as dense as air.
MIC is a toxic gas attacking the skin, eyes, respiratory systems and
internal organs. It is more lethal than Chlorine or Phosgene.

MIC is both volatile and unstable at higher temperatures and can

breakdown exothermically to give out large amounts of heat. For safe
handling, it must be maintained at about 0 C
 Bhopal Disaster
PRODUCT DESCRIPTION

Chlorine Cl2

Molecular Weight M = 71
Boiling point at atmospheric pressure b.p. = - 35 C.
It is a greenish yellow gas at room temperatures with vapour 2.5 times
as dense as air.

It is a toxic gas that attacks the lungs and other soft tissue.
 Bhopal Disaster
PRODUCT DESCRIPTION

Phosgene (Carbonyl Chloride) COCl2

Molecular Weight M = 99
Boiling point at atmospheric pressure b.p. = 8 C.
It is a volatile liquid or colourless gas at room temperatures with vapour 3.5
times as dense as air.

It is a toxic gas that attacks the lungs and other soft tissue.

Note both Chlorine and Phosgene were used extensively in WW1 as poison
gases.
 Bhopal Disaster
PRODUCT DESCRIPTION

Carbon Monoxide CO

Molecular Weight M = 28

It is a colourless, odourless, non-irritating, permanent gas slightly less dense

than air.
It is moderately toxic and kills by interfering with the blood oxygen transport
mechanism.
 Bhopal Disaster
CONTAINMENT DESCRIPTION
There were three identical MIC storage vessels all built from stainless
steel, type 304. The tanks were mounded in earth and the mound
covered with concrete. The disaster had its origin in one of these, tank
610.

The tank was horizontal, cylindrical in orientation with a diameter, D of

2.43 m and length, L of 13 m. Approximate Nominal Volume, V

V D 2 L 60 m3
4

Actual capacity would have been less than this taking into account
internal fittings, etc.; possibly 55 m3.
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CONTAINMENT DESCRIPTION MIC Storage Tank
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MIC STORAGE TANK

Picture shows the tank as it is today.
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MIC Storage Tank
Picture shows a section of the tank after the incident in an upturned
position.
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TANK PRESSURE / STRESS DESIGN

Normal Storage Pressure 0.2 bar g

Design Pressure 2.72 bar g
Hydraulic Test Pressure 4 bar g
Estimated Rupture Pressure 10 to 12 bar g

The membrane stress in the tank wall is proportional to the pressure; the
rupture pressure should correspond to the ultimate tensile strength of the
material (SS 304). Given the large margin between the normal storage
pressure and the rupture pressure, it is clear that membrane stresses will
be very low.
 Bhopal Disaster
TANK SAFETY FEATURES

A Nitrogen line was connected to the tank to transfer the product by inert
pressurization of the headspace. This could also be used to maintain a
positive pressure inside the tank and thus prevent the ingress of unwanted
liquids.

The tank was fitted with a pressure relief valve and rupture disc. The vent
line from the valve exhausted into a scrubbing tower filled with caustic soda
(NaOH). This would neutralize the MIC to form Sodium Isocyanate. Any
residual gas from the scrubber was sent to a 30 m tall flare stack where it
would be burned off.
 Bhopal Disaster
TANK SAFETY FEATURES

There was an external coiled jacket on the vessel through which coolant
(freon / chloroform) was recirculated. This was to keep the vessel contents at
0 C and thus prevent any adverse exothermic reactions occurring.

Tanks were not to be filled above the 50 % mark so that in the event of
dangerous chemical reactions occurring, solvents could be pumped in to
quench the reactions. The operating philosophy was that the tanks should
only hold the minimum amount of MIC necessary for Sevin production; they
were not to be used for stockpiling.
 Bhopal Disaster
ACCIDENT DESCRIPTION
Pipe Cleaning Procedure
As part of routine procedures, the pipes leading from the MIC distillation
column to the storage tanks were regularly flushed with pressurized water.
MIC and any associated products can be quite corrosive and could form
corrosion deposits in the pipe. These deposits would contaminate the MIC in
the tanks and could initiate unwanted reactions. During cleaning, valves in
the product lines were to be closed and a blank or slipblind placed in the
product line leading to the storage tank to prevent contamination.

However the valves, although closed, were not sealing properly because of
corrosion and the maintenance crew forgot about the blank. It appears that
about 1000 kg of water plus metal debris entered tank 610.

Assuming all the previously described safety features were operative, this
should not have been a catastrophic occurrence.
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ACCIDENT DESCRIPTION
Schematic view of pipe washing procedure indicating location of the
relevant valves and pipe blank.
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IN-OPERATIVE SAFETY FEATURES
The plant had been operating at a loss for the previous year due to lower
than expected demand for the product. The plant was not running
continuously but intermittently. A cost cutting programme of work had
been implemented:
The refrigeration system had been turned off about six months
previously to save on operating costs; this was the prime protection
system.
The caustic scrubbing tower was inoperative and the flare had been
partly dismantled.
Valves on the Nitrogen line were defective due to unsatisfactory
maintenance.
Lax operating routines meant that tanks were allowed to be filled above
the 50 % mark.
 Bhopal Disaster
TANK EXOTHERMIC REACTION
Tank 610 contained 42 tonnes of MIC. Exothermic chemical reactions
between the water and MIC began in the tank. Gases including Methyl
Amine, Carbon Dioxide, Phosgene and others were amongst the
products of these reactions and they pressurized the vessel. Corrosion of
the tank walls would also have been exacerbated and the released iron
may have catalysed further runaway reactions.

The pressure rose from the normal storage pressure of 0.14 bar g, up to
2 bar g and then onto 3.5 bar g and beyond. The temperature rose from
ambient (20 C) up to 60 C and beyond. The MIC liquid in the tank
began to boil vigorously and MIC vapour, under pressure traveled up
the pipes leading from the tank. A small leak of MIC developed at a
valve in one of the lines. The tank began to rumble and creak in its
concrete casing.
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TANK EXOTHERMIC REACTION
The main safety valve blew at a pressure in excess of 3.5 bar g and a jet
of MIC traveled up the scrubbing tower and escaped out the top. The
tank itself expanded with the heat, burst the concrete casing and was
ejected upwards to topple over. A second pipe then ruptured releasing a
second geyser of MIC.

From a mechanical point of view it is worth noting that the tank itself
did not rupture.
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TOXIC CLOUD DISPERSION
A vapour cloud about 100 m wide was formed above the plant consisting of the toxic
gases MIC, Phosgene, Hydrogen Cyanide and Methyl Amine. It was carried by a north-
westerly wind over adjacent parts of the town to the south of the plant where most of the
victims died from respiratory failure.

As a test exercise the vapour concentration surrounding the plant could be approximately
modelled by a Gaussian plume model

1 y 1 z
2

J 2 y 2 z
c x, y , z e e
yz u

A knowledge of wind speed is required for the model; on the night in question wind
conditions were light. Could take a wind speed of 5 m/s.
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TOXIC CLOUD DISPERSION

c Concentration of vapour in air kg/m3

J Rate of emission kg/s
y Cross wind diffusion coefficient m
z Vertical diffusion coefficient m
u Wind speed m/s
x Distance downwind of source m
y Distance left to right from source m
z Distance vertically upwards from source m
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TOXIC CLOUD DISPERSION
The diffusion coefficients depend upon the weather conditions at the time

Stability Category y z Valid Range

m m m
A (Unstable) 0.493x0.88 0.087x1.1 100<x<300
D (Neutral) 0.128x0.9 0.093x0.85 100<x<500
F (Stable) 0.067x0.9 0.057x0.8 100<x<500

The actual vapour concentrations predicted by the model could be compared to

the LD50 value; for example for phosgene this is 19 ppm.
 Bhopal Disaster
CONCLUSIONS

There were a number of clear contributory factors that caused this disaster.

1] Factory Siting
A plant producing a variety of very dangerous compounds was sited:
a) too close to a residential area
b) on the wrong side with respect to the prevailing wind.

2] Large Product Inventory

Total storage capacity of MIC was in excess of 150 m3. When dealing with
such toxic products, the amount at hand should always be minimized.
 Bhopal Disaster
CONCLUSIONS

3] Abandonment of Safeguards
Economic problems and the resultant pressure to save money lead to the
shutting down of vital safety systems. If the factory was uneconomic it would
have proved a more sensible option to shut it down.

4] Medical Unpreparedness
Not enough information on the toxicity of the factorys products and lack of
knowledge of treatment in the local hospitals. The factory should have been
much more pro-active in liasing with the municipal authorities in preparing an
emergency evacuation plan.