CHAPTER 5

FIRE & EXPLOSION

EP 419 Plant & Safety

Engineering
 Lecture Outline

• Fire triangle
• Flammability characteristics of liquid and vapor
flammability diagram,
• Ignition energy, auto-ignition,
• Detonation and deflagration,
• Vapor cloud explosion, BLEVE, dust explosion,
• Relief concept, location of relief and types of
relief.

2
 Hazards in Process Industries
• There are Three Major Hazards: Fire, Explosion, Toxic
Release

•Fire
–Impacts on plant, people and environment
–May also followed by toxic release

•Explosion
–Same as fire but more severe

•Toxic Release
–Impacts of people and environment. e.g. Bhopal
3
 Distinction between Fires & Explosions

• The major distinctions between fire & explosion is

the rate of energy release.

• Fire release energy slowly, whereas explosion release

energy rapidly.

• Fire can also result from explosion, and explosion can

result from fires.

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The Fire Triangle

Ms. Tan Jully 5

Fire will not occur if :

• Fuel is not present or is not present in sufficient

quantities

• An oxidizer is not present or is not present in

sufficient quantities

• The ignition source is not energetic enough to

initiate the fire.

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 Types Of Fire
• Pool Fire

• Jet Fire

• Flash Fire

7
 Flash Point vs Autoignition Temperature
Flash Point
The flash point is the lowest temperature at which a
substance vaporises into a gas, which can be ignited
with the introduction of an external source of fire.

Autoignition Temp
• In other words, the ignition temperature is the
lowest temperature at which a volatile material will
be vaporised into a gas which ignites without the
help of any external flame or ignition source.
8
 Pool Fire
• Liquid spilled onto the ground
spreads out to form a pool.

• Volatile liquid (e.g. petrol)

evaporate to atmosphere and
soon form flammable mixture
with air.

• Upon ignition, a fire will burn

over the pool.

• The heat vaporizes more fuel

and air is drawn in round to the
side to support combustion.

• Danger to people is by direct

thermal radiation and burn.
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 Jet Fire

• High pressure release of gas from a

vessel or pipeline ignites almost
immediately.

• This give rises to a giant burner of

flame length tens of meters.

• Danger from thermal radiation, heating

the content followed by pressure build
up causing ‘boiling liquid expanding
vapor explosion’ (BLEVE).

• Sometimes called Torch Fire

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 Flash Fire

• If spilled material relatively volatile (e.g. propane, butane, LPG) it would

still form a pool but evaporation would be much more rapid.

• If ignition did not take place immediately to form pool fire, then sizeable
vapor cloud would form, drifted away by wind, to form cloud within
flammable range.

• If found source of ignition, flash fire will occur. People at risk from
thermal radiation effects.

• Usually unexpected event and short duration

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• A flash fire is defined by CGSB 155.20-2000
and NFPA 2113 as:

• “A rapidly moving flame front which can be a

combustion explosion. Flash fire may occur in
an environment where fuel and air become
mixed in adequate concentrations to
combust...

• Occurs in relatively short periods of time,

typically less than 3 seconds.”

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Ms. Tan Jully 13
Second Degree Burn

14
Third Degree Burn

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 Explosion
• In general, there are 3 types of explosion;
Nuclear, Chemical & Physical.

• Mechanism:
Decomposition/Combination Rxn

Combustion gas (product) expands rapidly formed

shocked wave

Provide explosive effect

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• If explosion occurs in gas, the energy causes the gas to expand
rapidly, forcing back the surrounding gas and initiating a
pressure wave that moves rapidly outward from the blast
source
• Pressure wave contains energy~damage to surroundings
• For chemical plants much of the damage from explosions is due
to pressure wave
• A pressure wave propagating in air is called blast wave because
the pressure wave is followed by strong wind
• Shock wave or shock front results if the pressure front has an
abrupt pressure change~highly explosive material-TNT

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Deflagration is combustion that propagates through
a gas or across the surface of an explosive driven
by the transfer of heat at a speed less than the
speed of sound.

Detonation is a process of combustion in which

shock wave propagates through a body of material
at a speed excess the speed of sound.
19
 Types Of Chemical Explosion

• Dust Explosion

• Vapor Cloud Explosion

• Boiling Liquid Expanding Vapor

Explosion (BLEVE)

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 Dust Explosion
Due to the rapid combustion of fine solid particles.

• *If any of these five conditions is missing

there can be no dust explosion.

21
Imperial Sugar Explosion

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Vapor Cloud Explosion

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These explosions occur by a sequence of steps:

Sudden release of a large quantity of a

flammable vapor. Typically this occurs when
a vessel, containing a superheated and
pressurized liquid, ruptures.

Dispersion of the vapor throughout the

plant site while mixing with air.

Ignition of the resulting vapor cloud.

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 Factors Favoring Overpressures
of Vapor Cloud
1.Confinement
–Prevents combustion products escaping, giving higher local pressures
even with deflagration.
–Creates turbulence, a precursor for detonation (high shocked wave).

2.Cloud composition
–Highly unsaturated molecules are bad due to high flammable range,
low ignition energy, high flame speed etc.

3.Weather
–Stable atmospheres lead to large clouds.
–Low wind speed encourages large clouds.

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 Factors Favoring Overpressures
of Vapor Cloud

4. Source
–flashing liquids seem to give high overpressure
–vapor systems need very large failures to cause UVCE
–slow leaks give time for cloud to disperse naturally
without finding an ignition source
–high pressure gives premixing required for large
combustion
–equipment failures where leak is not vertically
upwards increases likelihood of large cloud
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• From safety standpoint:

The best approach is to prevent the

release of material. A large cloud of
combustible material is dangerous and
almost impossible to control, despite any
system installed to prevent ignition.

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 BLEVE (Boiling Liquid Expanding
Vapor Explosion)
• When BLEVE is initiated, the liquid
boils off rapidly producing a
reaction which turns parts of the
ruptured vessel into rockets which
can travel 2500 ft or more.

• The liquid can take fire if it is

flammable and burning material
can spread over a large area. If the
gas or liquid mixes with air a vapor
cloud explosion can occur.

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 Mechanism :
• External fire heats the content of a tank of
1 a volatile material

• Vapor pressure of liquid increases

2

• The structural integrity of the vessel is

3 weaken (as temperature increase)

The vaporizing liquid

will ignite/explode as
the tank ruptured.

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30
 Definitions
Auto ignition temperature - a fixed temperature above which a
flammable mixture is capable of extracting enough energy from
environment to self-ignite
Flash point - FP liquid is the lowest temperature at which it
gives enough vapor to form an ignitable mixture with air.

Fire point - lowest temperature at which vapor above liquid will

continue to burn once ignited, fire point is higher than FP.

Flammability limit (LFL and UFL) - vapor-air mixture will

only ignite and burn over well-specified range of compositions.
Common unit used - volume percent fuel (% of fuel plus air).

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Flammability Relationships

32
33
 Flammability Limits
• UFL & LFL for several common substances can be get from appendix in the
text book.
• Experimentally determined.
• LFL can be estimated from Flash Point:.

vapor pressure at flash point

LFL =
760 mmHg
Determine vapor pressure using Antoine Equation

Flammability Limits for Mixture

1
LFLmix = n
yi 1
∑
i =1 LFLi
UFLmix = n
yi
LFLi is flammability limit for component i ∑
i =1 UFLi
yi is mole fraction of i on combustible basis
n is the number of combustible species

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 Limiting Oxygen Concentration (LOC)
and Inerting
• The LFL is based on fuel concentration, but oxygen is also a key ingredient for combustion in
air. There is a minimum oxygen concentration required to propagate a flame. Thus we can
prevent combustion of a fuel by adding inert gases like nitrogen and carbon dioxide to reduce
the oxygen concentration. This is the basis of the common practice called inerting.

 Moles Fuel   Moles O 2 

MOC =   
 Moles Fuel & Moles Air   Moles Fuel 
 Moles O 2 
MOC = LFL  
 Moles Fuel 
Need to balance stoichiometry
Cm H xO y + zO2 → mCO2 + x H 2O
2
x y
z =m+ −
4 2
 Moles O2 
z= 
 Moles Fuel 
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In-Class Assignment 1:
Methanol FP=54°F, Vapor Pressure @ 54°F is 62 mmHg. Determine the flash
point of a solution that is 75wt% MeOH in water.

Solution:

Since only one component is flammable, can estimate mixture FP:

36
 In Class Assignment 2:
What are the LFL and UFL of a gas
mixture composed of 0.8% hexane, 2.0%
methane and 0.5% ethylene by volume.
% volume Mole fraction based LFL(vol %) UFL(vol %)
on combustible basis
Hexane 0.8 0.24 1.2 7.5
Methane 2.0 0.61 5.3 15
Ethylene 0.5 0.15 3.1 32
Total combustibles 3.3
Air 96.7

Solution ???
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 Flammability Limit Behavior
• In generally, the flammability limit dependent on temperature and
pressure.
• As temperature increases:
– Flammability range increases
– UFL increases, LFL decreases

• As pressure increases:
– UFL increases
– LFL mostly unaffected

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 In Class Assignment 3:
What is the UFL of a gas mixture
composed of 1% methane, 2% ethane
and 3% propane by volume at 50°C and
2 atm:

Data:

Component MW Heat of Combustion

(kcal/mol)
Methane 16.04 212.79
Ethane 30.07 372.81
Propane 44.09 526.74

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 Flammability Diagram

• Useful for:
- Determining if a mixture
is flammable.
- Required for control and
prevention of flammable
mixtures.

• Problems:
– Only limited experimental
data available.
– Depends on chemical
species.
– Function of temperature
and pressure.

40
Stoichiometric line
• All stoichiometric combinations of fuel plus oxygen.
• The combustion reaction can be written in the form
Fuel + zO2  combustion products

where z is the stoichiometric coefficient for oxygen.

• The stoichiometric line is drawn from this point to the pure

nitrogen apex.
Flammability diagram
Limiting O2
Concentration:
LOC
Vol. % O2 below
which combustion
can’t occur

FLAMMABLE
MIXTURES UFL

LFL

Air line:
79% N2
21% O2
There is a methane Locate the mixture composition
mixture composed of 40% point at the methane ternary
flammability diagram provided.
methane, 30% O2, and Is this mixture flammable?
30% N2
The mixture
composition falls
within the
flammable
envelope, so it is
flammable.

FLAMMABLE
MIXTURES
There is a methane How to make it non-flammable
mixture composed of 40% by adding nitrogen for inertion?
methane, 30% O2, and So in order to get the
30% N2 mixture non-flammable,
the nitrogen should be
increased from 30 to 50%.

FLAMMABLE
MIXTURES
Safe Dilution of a Flammable Gas Mixture
A vessel contains a gas mixtures composed of 50% methane and
50% nitrogen. If the mixture escapes from the vessel and mixes with
air, will it become flammable?
The initial dilution status is shown as
point B.
If released into air, the final status of
dilution is pure air (Point A).

B
The mixing line BA is crossing
the flammable zone, so there
is a danger of explosion
FLAMMABLE during the mixing process.
MIXTURES

A
Safe Dilution of a Flammable Gas Mixture
A vessel contains a gas mixtures composed of 50% methane and
50% nitrogen.
How to make it strictly non-flammable during the dilution process?
In order to avoid the flammable zone
during the mixing, a tangent line is
drawn passing the air point A, which
is called the dilution line.
The cross point with
B
Nitrogen axis is point C.
That means, the initial
mixture has to be diluted to
point C (non-ignitable) by
FLAMMABLE
C nitrogen dilution first, then it
MIXTURES
can be allowed to be mixed
with air without any danger
A of ignition (or explosion).
 Relief Concepts
Pressure relief systems are required for the following
reasons:
 To protect personnel from the dangers of over
pressurizing equipment.
 To minimize chemical losses during pressure upsets.
 To prevent damage to equipment.
 To prevent damage to adjoining property.
 To reduce insurance premiums.
 To comply with governmental regulations.
 Line of Defense
1. Inherent Safety.

2. Good process control.

3. Installation of relief system.

Definitions that are commonly used within the chemical
industry to describe reliefs are given in the following:
Set pressure
The pressure at which the relief device begins to activate.

Maximum allowable working pressure (MAWP)

The maximum gauge pressure permissible at the top of a vessel
for a designated temperature.

This is sometimes called the design pressure.

Vessel failure typically occurs at 4 or 5 times the MAWP, although

vessel deformation may occur at as low as twice the MAWP.
Operating pressure
The gauge pressure during normal service, usually 10% below the
MAWP.
Accumulation
The pressure increase over the MAWP of a vessel during the relief
process. It is expressed as a percentage of the MAWP.
Overpressure
The pressure increase in the vessel over the set pressure during the
relieving process.
Overpressure is equivalent to the accumulation when the set
pressure is at the MAWP.
It is expressed as a percentage of the set pressure.
Backpressure
The pressure at the outlet of the relief device during the relief
process resulting from pressure in the discharge system.
Blowdown
The pressure difference between the relief set pressure and the
relief reseating pressure.
It is expressed as a percentage of the set pressure.

Maximum allowable accumulated pressure

The sum of the MAWP and the allowable accumulation.

Relief system
The network of components around a relief device, including the
pipe to the relief, the relief device, discharge pipelines, knockout
drum, scrubber, flare, or other types of equipment that assist in the
safe relief process.
 Location of Reliefs
Guidelines for specifying Relief Positions
o All vessels need reliefs, including reactors, storage tanks, towers,
and drums.
o Blocked-in sections of cool liquid-filled lines that are exposed to
heat (such as the sun) or refrigeration need reliefs.
o Positive displacement pumps, compressors, and turbines need
reliefs on the discharge side.
o Storage vessels need pressure and vacuum reliefs to protect
against pumping in or out of a blocked-in vessel or against the
generation of a vacuum by condensation.
o Vessel steam jackets are often rated for low-pressure steam.
Reliefs are installed in jackets to prevent excessive steam
pressures due to operator error or regulator failure.
Example
Specify the location of reliefs in the simple polymerization reactor
system illustrated in Figure 8.5.
The major steps in this polymerization process include
(1) Pumping 100lb of initiator into reactor R-1.
(2) Heating to the reaction temperature of 240 °F
(3) Adding monomer for a period of 3 hr, and
(4) Stripping the residual monomer by means of a vacuum using valve
V-15.
Because the reaction is exothermic, cooling during monomer addition
with cooling water is necessary.
Solution
a. Reactor (R-1):
A relief is installed on this
reactor because, in
general, every process
vessel needs a relief. This
relief is labelled PSV-1 for
pressure safety valve 1.
Solution

b. Positive displacement
pump(P-1):
Positive displacement
pumps are overloaded,
overheated, and damaged
if they are dead-headed
without a pressure-
relieving device (PSV-2).
This type of relief
discharge is usually
recycled back to the feed
vessel.
Solution

c. Heat exchanger (E-1):

Heat exchanger tubes can
rupture from excessive
pressures when water is
blocked in (V-10 and V-11
are closed) and the
exchanger is heated (by
steam, for example). This
hazard is eliminated by
adding PSV-3.
Solution

d. Drum (D-1):
Again, all process
vessels need relief
valves, PSV-4.
Solution

e. Reactor coil:
This reactor coil can be
pressure-ruptured when
water is blocked in (V-4,
V-5, V-6, and V-7 are
closed) and the coil is
heated with steam or
even the sun. Add PSV-5
to this coil.
Types of relief
 Specific types of relief are chosen for specific
applications, such as for liquids, gases, liquids
and gases, solids and corrosive materials;
they be vented to the atmosphere or
containment systems (scrubber, flare,
condenser, and incinerator).

 In engineering terms the type of relief device

is specified on the basis of the details of the
relief system, process conditions, and
physical properties of the relieved fluid.
Spring Operated Valve
 The adjustable spring
offsets the inlet pressure
 The relief set pressure is
usually specified at 10%
above the normal
operating pressure.
 To avoid the possibility of
an unauthorized person
changing this setting, the
adjustable screw is covered
with a threaded cap.
 Balanced-bellow Valve
 The bellows on the
backside of the valve seat
ensures that the pressure
on that side of the seat is
always atmospheric.
 Valve will always open at
the desired set pressure.
 However, the flow through the balanced-bellows relief
is proportional to the difference in pressure between
the inlet and the outlet of the valve.
 Therefore, the flow is reduced as the backpressure
increase.
 Rupture Disc
 Specifically designed to
rupture at a specified relief
set pressure.
 They usually consist of a
calibrated sheet of metal
designed to rupture at a well-
specified pressure.

 They are used alone, in series,

or in parallel to spring-loaded
relief devices.
 They can be made from a variety of materials, including
exotic corrosion-resistant materials.