Styrene Vapour Release Incident at LG Polymers: Harikrishnan M

Styrene Vapour Release Incident a
LG polymers
Harikrishnan M
AIM
• Incident analysis of Styrene vapour release at LG polymers,
Vishakhapatnam.
• Identify the root causes of the incidents.
• Analysis of Emergency Management.
• Learning from the Incidents.
• Management of Change.
Incident Description
 On 7th May 2020, around 3:00 AM
uncontrolled release of Styrene vapour
occurred at LG Polymers India Pvt.
Ltd., Vishakhapatnam.
 Styrene vapours spread beyond the

factory premises, affecting the
population of five villages / habitations.
 Incident lead to 12 citizens losing their

lives and 585 citizens being
hospitalized.
 The Incident was a Major Accident as

per MSIHC rules.
Major Accident as per MSIHC
rules,1989
 LOSS of Life inside/outside
 10 or more injuries inside
 1 or more injuries outside
 Release of Toxic Chemicals Onsite emergencies
 Fire
Offsite emergencies
 Explosion
 Release of Toxic chemicals Damage to Equipment
 Spillage of hazardous chemicals Environmental effects
LG Polymers
 The Unit was first started in 1961 for

manufacturing alcohol from molasses.
 In 1967,the unit was modified for
Polystyrene & Co-Polymer.
 The company was taken over by current
management, LG Chemicals (South
The incident took place in the M6 tank
Korea) in 1997.
used for storage of Styrene Monomer.
 The range of products being
manufactured are: Operating Capacity of 2450 KL.
 General Purpose polystyrene (GPPS)
D: 18 m & H:12.15 M
 High Impact Polystyrene (HIPS)
 Expandable Polystyrene (EPS)
PESO license for Class B petroleum.
 Engineering Plastics Compounds
 Major Raw Materials:

 a) Styrene Monomer
 b) Ethyl Benzene
What is Styrene ?
 Organic compound with the formula C8H8.

 Derivative of Benzene.
 Colourless liquid at normal temperature.
 Used in the Production of Polystyrene, Acrylonitrile-Butadiene-
Styrene rubber, and many other polymers
Critical Properties
 Explosive range: 1.1 % to 7%

 Flash point: 31°C
 Boiling point: 145 °C
 Auto ignition temperature: 490 °C
 Highly reactive and can polymerise(exothermic reaction)
 Runaway reaction occur at 65°C.
 STEL 100PPM, TLV: 50PPM, IDLH:700PPM
 Causes severe eye, skin and respiratory irritation, CNS depression, nausea, vomiting etc.
on short term exposure
 Carcinogenic (2A)
Polymerization of Styrene
 Rate of Polymerization Temperature

 Polymerization reaction is exothermic (17.8 Kcal/gm-mole).
 Polymerization is initiated by
 Heat
 Reaction with peroxides
 Lack of inhibitors
 Lack of Oxygen (8 PPM)
 Runaway Polymerization occurs at 65 °C and the temperatures

may then exceed 145 °C.
Controlling Polymerization
• Polymerisation is controlled by adding inhibitors which

 Breaks the Free radical Chain formation.
 Reacts with the Oxidants in styrene(anti oxidant)
 Polymerisation is controlled in normal circumstances by adding

low temperature inhibitor substance like p-tert-butyl catechol
(TBC).
 Ethyl Benzene/ toluene can be added to dilute and retard the rate
of polymerization and reduce viscosity.
 For high temperatures, inhibitors like Tertiary Dodecyl
Mercaptan (TDM) and n-dodecyl mercaptan (NDM) etc. can
inhibit the polymerisation of Styrene
Tank Design
Tank Design
• The Tank was old and was not lined.
• The roof of the tank was cone type and was supported in the interior. This resulted in
Condensation of styrene vapours on the internal structure and resulted in formation of
stalactite's.
 The gases were directly vented to the atmosphere.
 Tank cleaning was last done in 2015 , that resulted in the accumulation of
contaminants, which acted as catalyst initiating polymerization of Styrene.
 The Tanks were insulated. This prevented heat dissipation from the tank during the
runaway reaction.
Change in Design: Modification
Due to Stalactites formation, the float on the tank got stuck and had to be
removed This called for a design Change.(DEC 2019)
Originally, the tank was having a swing The new piping arrangement provided for the
pipe arrangement to discharge the cooled cooled Styrene monomer liquid to be
Styrene from the recirculation and delivered at the bottom of the tank through a
regeneration unit at the top of the tank dip leg arrangement.
Before
Change in Design
 The Modification was done without any Risk assessment & PESO approval
was not obtained.
 Before the modification:

“ The denser cold Styrene moves down towards the bottom by gravity and
natural convection, ensuring a circulation in the tank”.
• After the modification:

“The modification in piping design disturbed the Styrene recirculation system
that led to significant thermal stratification.”
The top level of the Styrene monomers now experienced higher temperatures
than the lower monomers.
Temperature Monitoring
 The temperature measurement in the Tank was restricted to bottom zone only.
 The temperature measurement (RTD) probe was located close to the discharge
port.
 The recorded temperature in the tank on the day before the incident was 16-17 C
which was normal.
The temperature measurement were confined to bottom zone and the temperatures at
bottom and middle levels were unknown.
Hence the System was unable to identify “Thermal Stratification”

Refrigeration of Tank
 Max temp in Styrene storage tanks should not exceed 25°C. (Chevron Philips18 and
Plastic Europe19).
 The normal operating temperature is 10-18°C. If temperature reaches 20°C cooling

should be done.
 Refrigeration system was available for the tank, but it was operated in Manual mode.
 For refrigeration the suction was taken from the N13 port (which is located 100 mm
from the bottom of the tank).
 The cooled styrene monomer was then introduced through the dip leg arrangement
(300 mm from the bottom)
For a location like Vizag, where the average temperature is 35°C, Continuous refrigeration
system is essential.
Preferably an Automated Refrigeration system coupled with temperature sensors are
preferred.
Refrigeration of Tank
R – 22 is difluoro, mono-chloro
methane, also known as HCFC-22 or
Freon 22. was used as the
refrigerant.
The heat exchanger was also in a

poor condition and the tubes in the
heat exchanger had developed pin
holes.
The capacity of the recirculation

pumps where also found to be
inadequate.(30 m3/hr for 2250 m3).
TBC Monitoring
 Inhibitors should be added below 10 PPM to maintain adequate inhibition. Normal
levels in tank will be 10-15 ppm.
 TBC addition was below the requirements.
 Monitoring of TBC levels is very Significant and the procedure was very irregular
in the Unit.
 TBC analysis of samples from the bottom layer were only carried out. Top levels
were not analysed.
 Stocks of TBC & other high temperature inhibitors like TDM & NDM were
limited.
Since TBC levels were monitored only at the bottom, the TBC stratification at the top
layers went unnoticed. The TBC levels at the top reduced to less than 4 PPM.
Safety Lapses
 Company was shutdown during lock down. They did not consider the
idling conditions in the tank.
 No SOP for shutdown and start-up.(NO PSSR)
 Log books/Data books do not have details of activities carried out.
 No daily Sampling.
 No System for measurement of dissolved oxygen in the tank.
 Improper Onsite emergency plan.(Styrene gas leak scenario was not
considered)
 Improper Safety Management Systems, No proper Engineering drawings,
HAZOP studies etc. were available.
 Incompetent top, middle and low management.
Final analysis 800 tons of styrene escaped into the
atmosphere
Polymerization due to presence of
Thermal radical Polymerization

TBC depletion
Temperature Monitoring
Polymerization
Catalyst
Operating Procedures &

Process Safety
Incompetent Management
Tank Design
Execution Of Onsite & Off site Emergency plan
 As per the CCTV records, Styrene vapours were first visible at 2:42 AM.
2:42 AM 2:53 AM
 The 4 Gas detectors beneath got activated at 2:53 AM. The delayed response can be due to
 Positioning of the Sensors.
 The alarms were set for 20% of LEL.
The gas detector should have been set based on STEL limit (100PPM) down the
temperature.
Execution Of Onsite & Off site Emergency plan
 At 3:03 AM, the Night duty officer responds to the emergency.

 He tries to operate hydrant but fails since the gas has already spread to around 300 M
from the tank. Most of the Staff in duty were in Panic Mode.
 The Emergency actions were initiated only after the Senior Management officials arrived
at the Spot (3:30 AM)
 The Scenario became Level 3 incident at 3:30 AM and Fire tenders and district police
Failure from the First responders
 The Onsite Emergency Plan of the Unit was prepared as per MSIHC rules.
 The Emergency plan however did not cover Toxic gas scenarios and was based on Fighting
Fire incidents.
 The First responders (Shift in charge & Night duty officer) approached the scenario like a
Fire incident. Foam Pourers, Sprinklers were used.
 Addition of temperature inhibitors into the tank for controlling the polymerization reaction
was started late only after the senior management officials reached the spot.
Ethyl Benzene was available and could have been pumped to the bottom of the tank and
then started the Refrigerant system. This could have brought down the temperature.0 C.
Failed Primary Response
 Due to the failed primary response, the use of short

stopper chemicals/ethyl benzene could not be used.
 NDM &TDM was added to the tanks for controlling the
polymerization reaction.
 TBC was not available in the Unit. By the time TBC was
airlifted the temperature of the tank had already crossed
157 C.
Other lapses in Emergency Management
 Emergency Siren was not sounded.
 Wind direction was not observed, downwind alert was not

given.
 Inadequate Mock drills
 Failure to take up emergency Evacuations in neighbouring

habitations.
 Failure to conduct awareness in neighbourhood

Learnings From the
Incident
How to avert such incidents?
 Keep industries away from populated areas
How to avert such incidents
 Conducting regular Hazard & Risk assessment studies.
 Keeping adequate number of Detectors for identifying
leak/Spillages.
 Strict implementation of onsite and off site Emergency Plan.
Coordination with local crisis groups.
 Conducting regular internal and external Safety Audits.
 Establishing buffer zones around industries.
Implementation of Management of Change (MOC)
 MOC is one of the Elements in Process Safety Management.
 Analysis of a majority of the Major Accidents points towards

“Change”.(eg: Flix borough Disaster)
 The Change can be an alteration to any component, variable or

property within an existing system.
 MOC ensures that

 No Unintended Hazard is introduced
 Risk is Minimized
When MOC is Required ?
 Change of Process/technologies
 Change of Catalysts
 Change of Chemicals
 Change of Personnel
 Change of hardware/ software
 Change in operating procedures
 Change in working Environment
The MOC Process
STEP 1:
STEP 2:
The Idea of MOC
Design Philosophy &
 Is it necessary? Approval
 Is it Economical? Process Design Mechanical Design
 Block Flow  Engineering
diagram/Process drawings, P&ID.
 Is there a better Flow diagram
alternative?  HSE analysis (PHA)
 Review of standards
& regulatory
 Any Impacts on requirements
 External/Internal
Health, Safety & review
Environment.?
The MOC Process
STEP 3:
Execution of the MOC JOB
STEP 4:
Training of Operational/Maintenance Personal
STEP 5:
Commissioning
STEP 6:
Handing over/ take over
STEP 7:
Post Commissioning Review
Thank You

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Styrene Vapour Release Incident a

 Styrene vapours spread beyond the

 Incident lead to 12 citizens losing their

 The Incident was a Major Accident as

 The Unit was first started in 1961 for

 Major Raw Materials:

 Organic compound with the formula C8H8.

 Explosive range: 1.1 % to 7%

 Rate of Polymerization Temperature

 Runaway Polymerization occurs at 65 °C and the temperatures

• Polymerisation is controlled by adding inhibitors which

 Polymerisation is controlled in normal circumstances by adding

 Before the modification:

• After the modification:

Hence the System was unable to identify “Thermal Stratification”

 The normal operating temperature is 10-18°C. If temperature reaches 20°C cooling

The heat exchanger was also in a

The capacity of the recirculation

 TBC addition was below the requirements.

Polymerization due to presence of

Thermal radical Polymerization

Operating Procedures &

 At 3:03 AM, the Night duty officer responds to the emergency.

 Due to the failed primary response, the use of short

 Wind direction was not observed, downwind alert was not

 Inadequate Mock drills

 Failure to take up emergency Evacuations in neighbouring

 Failure to conduct awareness in neighbourhood

 MOC is one of the Elements in Process Safety Management.

 Analysis of a majority of the Major Accidents points towards

 The Change can be an alteration to any component, variable or

 MOC ensures that

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