TSE101

Technical Safety Engineering Foundation

1.4 Reactive Hazards

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GSNL-HPTS

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2011

LEARNING OBJECTIVES
Be able to able to:
Define

reactive hazards and runaway reactions

Recognise

some situations in which reactive hazards and runaway

reactions may occur

Describe

the roles of thermodynamics, kinetics and fluid flow in the

assessment of reactive hazards

Identify

resources who can help with reactive hazards at your facility

or in your project

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REACTIVE HAZARDS DEFINITION

Also known as:

Reactive chemical hazards

Chemical reactive hazards

Runaway reaction hazards

Shell Definition:
Reactive Hazards are chemical reactions that can lead to large and
rapid changes in temperature and/or pressure

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RUNAWAY REACTIONS
A runaway reaction is a chemical reaction that exceeds the
temperature and/or pressure capabilities of the vessel that contains it.
Some bad things that can happen when a runaway reaction occurs
include:

Vessel overpressure (vessel bulging, rupture, BLEVE)

Vessel over-temperature (wall weakening, rupture, solid polymer formation

and plugging, failure at connections)

Vessel under-temperature (solid plugging, embrittlement)

Note: Unlike a fire, a casual observer cant see the temperature or

pressure rise (or poisonous gas evolution), so there is no warning of the
danger.
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TEMPERATURE OF NO RETURN
The temperature of no return is the lowest temperature where the
heat generated by the runaway reaction in the vessel exceeds the
cooling capacity.
Example: Cooling coils in a reactor have a maximum duty of 100 kW.

When the rate of heat generated by a reaction exceeds 100 kJ/s

(kW), the temperature in the vessel will start to rise.
Recalling your kinetics . many reactions accelerate when the
temperature rises, so the runaway reaction will start to go faster and
faster. Temperature in the reactor can start rising exponentially.

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USEFUL DEFINITIONS WHAT IS WHAT?

Time to maximum rate (TMR)
Time it takes to get to the top event

Adiabatic induction time (tad)

TMR without taking heat loss or external heat input into account

Temperature of no return (TNR)

Legend:
tad = adiabatic induction time
Cp = heat capacity
A = pre-exponential factor
Q = heat of reaction
R = gas constant
T0 = start temperature
EA = activation energy

Temperature at which heat generation rate exceeds cooling capacity. Restoring cooling when
temperature is above TNR will only delay the top event

Critical ambient temperature

Ambient temperature at which self-heating will start (comparable with TNR, mainly used for storage)

Onset temperature
Lowest temperature the reaction is detected in laboratory equipment (temperature depends on
sensitivity of the equipment, e.g. 0.02 C/min)
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EXAMPLES

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SOME PREVIOUS INCIDENTS INVOLVING RUNAWAY

REACTIONS
Reactive Hazards incidents have high consequences compared to
other incidents in industry
Seveso 1976

Dioxin (toxic) release (injuries, major clean-up operation required). Incident

invoked new regulation (Seveso guideline, implemented in Europe as e.g.
COMAH, UK or BRZO, NL)

Bhopal 1984
Methyl isocyanate hydrolysis (> 2500 fatalities, divestment). Union Carbide
was bought by Dow

Allentown, PA 1999
Hydroxylamine decomposition and explosion (5 fatalities)

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SHELL STANLOW FLUOROAROMATICS INCIDENT

March 1990

Plant upset (water ingress)

Unknown chemistry

Runaway reaction

T & P spike overwhelmed reactor

Shrapnel traveled over 500m

6 employees were injured

1 fatality

Total destruction of the unit

Business shut down

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EXAMPLES OF REACTIVE HAZARDS-BASED INCIDENTS

WITHIN SHELL
Belpre (1994) Explosion in the polymer unit, leading to 3 fatalities
and total destruction of unit.
Excessive butadiene charge / too little solvent charged to Step II
polymerization reactor.
Geismar SHOP I/D (2002) Catalyst explosion (NaK + H2O),
leading to 1 fatality.
Berre Lower Olefins (1990) Cold Box explosion due to heating of
blue gums formed by the combination of NOx and olefins.
Geismar SHF (1997) Methanation reaction (CO + H2) leading to
local temperatures above 750 C and piping damage.

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ISSUES TO CONSIDER IN REACTIVE HAZARDS

Thermodynamics heats of absorption, heats of reaction

Can this reaction even occur?

What amount of heat could be generated? Could that exceed the design
temperature?

Kinetics reaction rates

How fast will this reaction occur?

Is the reaction temperature and/or concentration dependent?

Fluid flow choked flow, two-phase flow

Is there some way to safely release the products of the runaway reaction
(rupture disk, safety relief valve (SRV))?

Is the relief device big enough to let the products out fast enough? Or will
it overpressure and fail the vessel?

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TYPICAL BARRIERS FOR PREVENTING CATASTROPHIC

EVENTS
Overpressure protection (e.g., relief device)

Reactivity must be included

Potential for two-phase flow (i.e., Champagne bottle)

Effluent handling considerations

Emergency depressuring
Instrumented Protective Functions (e.g., high P trip or high T trip)
Operator response (e.g., initiating emergency cooling)

Normal process control

In an IDEAL world, we wouldnt need these barriers . . .

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UPSETS CAN LEAD TO UNEXPECTED REACTIONS

However, we dont live in an ideal world & things do GO WRONG!
Common upsets include:

Loss of cooling

Failure of temperature or pressure control

Loss of flow

Flow maldistribution of liquids through catalyst beds

Power failure

These upsets can lead to operation outside of the normal operating

window:

Increased residence time (e.g., loss of flow)

Increased temperature (e.g., loss of cooling water)

Increased concentration of reactants (e.g., loss of recycle)

Any of these scenarios can lead to a runaway reaction

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MANAGING REACTIVE HAZARDS WITHIN SHELL

Work process includes

Review process data

Identify and assess reactive chemistry

and binary incompatibilities

Collect information on previous incidents and

near misses

Scenario identification and development

(may include dynamic simulation)

Semi-quantitative risk assessment (LOPA)

Advice on measures to reduce the residual risk

Reactive relief evaluation

Never assume Ask the Experts. Reactive Hazards Team of

Specialists to be contacted via: TechHSEhelp@ shell.com
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SUMMARY
Reactive Hazards are chemical reactions that can lead to large and
rapid changes in temperature and/or pressure
Reactive Hazards incidents have high consequences compared to
other incidents in industry
Thermodynamics, kinetics and fluid flow must be considered when
assessing reactive hazards
Typical barriers to prevent catastrophic events
Common upsets that could potentially lead to a catastrophic event

Managing reactive hazards within Shell: work process

Never assume Ask the Experts. Reactive Hazards Team of
Specialists to be contacted via: TechHSEhelp@ shell.com

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