Chemical Reaction Safety: Paul Sharratt 19 August 2019

Chemical Reaction Safety
Paul Sharratt
19th August 2019

Chemical Reaction Safety
Safety and Chemical Reactions
Case Studies
Key Learning
2
Safety and chemical reactions
• Chemicals may store a large amount of energy that can be released in a variety of
ways
– Chemical reactions often release a lot of energy as they progress
– Accidental mixing of chemicals may give unwanted reactions
– Some materials are shock-sensitive and may decompose violently
• Normally we design and operate processes to avoid or deal with the energy release
Other
materials
Shock heat
3
Safety problems from chemical reactions
• If we fail
– To understand the process well enough
– To design appropriate controls
– To operate the process within a safe envelope
heat
The consequences can be disastrous
4
Types of reaction hazard
• Self-reactive chemicals sensitive to heat or shock

– Heat or impact initiates rapid decomposition
• Runaway reactions
– The rate of heat removal doesn’t match generation, so the reaction
accelerates and releases even more heat. Additional reactions may kick in
as the temperature rises.
• Reaction between incompatible materials
– Incompatible materials come in contact through error or equipment failure
5
Safety problems from chemical reactions
CSB in The US looked at 167 serious
reactive incidents over January 1980 - June
2001.
• These caused 108 deaths, hundreds of
Loss of reaction control Toxic injuries, and significant public impacts.
opens up multiple routes release
• 70 percent of reactive incidents occurred in
to injury and property the chemical manufacturing industry, with 35
damage percent due to runaway reactions.
• 42 percent of reactive incidents resulted in
fires and explosions, another 37 percent
caused toxic emissions.
Excessive • Many reactive incidents occurred at small
energy manufacturing sites.
release
Flammable
Explosion
release
6
Root causes of reaction accidents
• We didn’t know enough about the reactions before we operated at a

dangerous scale
• We didn’t implement sufficient or appropriate measures to control
foreseeable problems
• We let the controls lapse and/or operated outside the safe envelope
7
Case studies
Case studies
• Many widely known examples

– Bhopal, Seveso
• Other examples will be given here, picked because of the potential
learning for Singapore
• Sources: US Chemical Safety and Hazard Investigation Board,
Singapore WHSC
9
Ignorance is not bliss, experience is
not safety…
Polymer coatings manufacture
• Synthron (Morganton, North

Carolina) was a manufacturer of
acrylic coatings and paint additives
• They carried our polymerization
reactions in a 1,500 gallon reactor
• Solvents, acrylic monomers and
initiators were mixed to various
recipes
– The reaction was heated with an
initiator to start it
– Once established, heat was removed
continuously by condensing
solvent/monomer vapour and
returning liquid to the reactor
– Excess heat could be removed by
putting cooling water through the
jacket
11
Operating approach
• Small team ran the plant

– None had any prior background in polymers
– None in the company for more than 9 months
• No process hazard analysis or reaction risk assessment was used
• Typical process approach was to add solvent, half the monomer and
initiator at the start then add rest of reactant slowly
– Previous manager had scaled up new products based on past experience
– Processes “evolved” by incremental changes, backing off if the condenser
seemed to be struggling (flooding or pressure build-up)
• Various lax operating practices
– Only bolting 4/18 bolts used to secure the vessel manway
– Plant maintenance was limited
– Poor safety culture, training, documentation and planning
– Ineffective management of change processes
12
The incident
• A customer placed an order for 12% more than a standard batch
• The manager avoided making two part batches by modifying the process
– Using extra monomer in the first charge (increase amount and conc.)
– Reduced solvent quantity (reduced thermal mass)
– Used more higher boiling solvent (increased reaction temperature)
• Result was to increase the peak reaction rate by a factor of 2.3
• The condenser could not cope and the pressure rapidly rose
• Solvent escaped through the inadequately sealed manhole into the factory
• Solvent ignited
13
Outcome
• 1 fatality, 14 injured (2 seriously)

• Company filed for bankruptcy
14
Learning from the accident
• Know your reaction

and your plant
• Make sure your
people, plant and
methods are in good
working order
• Manage change
effectively
15
Change needs thought, and good
memory…
Methomyl production
• Bayer CropScience
operated a plant to
manufacture Methomyl at
Institute West Virginia
• Hazardous process
involving several
dangerous materials
– Chlorine
– Phosgene,
– MIC
– Methyl Mercaptan
• Risk of exothermic
Methomyl decomposition
well known and understood
17
Methomyl production
• The post-filtration liquor was

flashed to recover solvent
• The flasher bottoms were
heated in the Residue
Treater to decompose
residual methomyl
– Methomyl decomposes
exothermically
– Methomyl kept below 0.5%
concentration by diluting in
solvent and treated residue
– Higher concentrations were
known to generate too much
heat (1% limit)
• The treated residues were
used as a fuel
Should operate
<80°C Should operate
>130°C
18
Changes in plant operations
• Various operational changes were being made or had occurred

before the accident
– Technical support for operations had been “thinned” with only one
“technical adviser” covering Methomyl and another plant on day shifts
– An ageing control system was being replaced with a modern DCS system
– Various plant items were being replaced
• Assessment of the impact of the changes had been limited and of
poor quality
– Hazard assessment sessions had been brief and inappropriately staffed
– Training of staff in use of the new control system had not been fully
effective
– A pre-existing culture of poor work practice had not been addressed
• The plant was being restarted
19
A catalogue of errors
Operators were working from draft
SOP not including new control system
The crystallization step

failed but operators carried on.
Lab analysis of 4% Methomyl in liquor
ignored in face of other problems
Liquor sent to centrifuges –

and passed straight to Flasher
Residue Treater not pre-charged

with solvent or pre-heated enough
Methomyl content of Flasher

residue 40%, not 22% Samples not taken to test
for Methomyl content
Trips defeated to allow transfer into
Cold Treater (65°C, not 130°C), and
with low recirculation flow through
heat exchanger 20
The event
• On the evening of 28th August a rapid pressure rise was noted in the
Residue Treater
• Two employees dispatched to investigate
• As they approached the unit it exploded violently
• About 1 tonne of toxic residues and solvents sprayed out and ignited
• Debris was thrown over a wide area
Circulation, heating started Explosion
Circulation fails
21
The accident
• The remains of the thermal

treater ended up in a
neighbouring unit
• 2 people dead
• 8 people inhaled toxic gas
• 40,000 advised to remain
indoors
• Property damaged by
flying debris at distances
up to 11km distance
22
Some luck prevented
worse problems
• Methyl isocyanate (MIC)

stored in above-ground
storage
– Surrounded by protective
cladding
• Some debris struck the
storage
• Fortunately, none struck
the protruding relief valve
or transfer piping that
could have released the
contents
23
Learning
• After any process or plant change there needs to be an appropriate

and competent Safety review
• Commissioning can’t be rushed
– It’s very dangerous to be fixing installation problems while trying to operate
– Having people available in commissioning who understand the key safety
issues is essential
24
Some things are better kept apart…
Specialty chemicals manufacture
• Hydrogen peroxide was being pumped down a line during a

troubleshooting activity.
• A branch from the line, leading to a reactor and settler tank, had not
been isolated properly
• Peroxide entered the reactor where it found residual sulphuric acid
and isopropanol.
• The mixture reacted violently, raising the pressure until the reactor
burst
• Fortunately, nobody was close at the time
26
The result of mixing incompatible chemicals
Remains of
the Reactor lid
27
The reaction
• Concentrated Sulphuric Acid and Hydrogen Peroxide react to form

“Pirahna Solution” – which is notorious as a rather unsafe cleaning
agent
“Piranha solution is very dangerous, being both

strongly acidic and a strong oxidizer. Solution that
is no longer being used should never be left
unattended if hot. It should not be stored in a
closed container. Piranha solution should not be
disposed of with organic solvents (e.g. in waste
solvent carboys), as this will cause a violent
reaction and a substantial explosion.”
(Wikipedia)
28
Root causes
• A suitable risk assessment had not been performed

• The operators had limited knowledge of the routes taken by pipes (ie
where the peroxide could go)
• Equipment (reactor and settler) were not equipped to deal with the
situation
• Little instrumentation
• Relief systems too small
• Cooling system off
• Poor operational practices (leaving chemicals in vessels not in
operation)
29
Key Learning ….
Learning
• Assess thoroughly
– Including both planned reactions and credible deviations
(e.g. side reactions and byproducts)
– Process change / maintenance can introduce additional
hazards
• Design to eliminate or mitigate risks

• Operate within the defined envelope / basis of safety
• Manage change effectively
31
Thank you

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Chemical Reaction Safety

19th August 2019

Safety and Chemical Reactions

The consequences can be disastrous

• Self-reactive chemicals sensitive to heat or shock

• We didn’t know enough about the reactions before we operated at a

• Many widely known examples

• Synthron (Morganton, North

• Small team ran the plant

• 1 fatality, 14 injured (2 seriously)

• Know your reaction

• The post-filtration liquor was

• Various operational changes were being made or had occurred

The crystallization step

Liquor sent to centrifuges –

Residue Treater not pre-charged

Methomyl content of Flasher

Circulation, heating started Explosion

• The remains of the thermal

• Methyl isocyanate (MIC)

• After any process or plant change there needs to be an appropriate

• Hydrogen peroxide was being pumped down a line during a

• Concentrated Sulphuric Acid and Hydrogen Peroxide react to form

“Piranha solution is very dangerous, being both

• A suitable risk assessment had not been performed

• Design to eliminate or mitigate risks

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