Fire & Explosions

Introduction
• 3 most common accident in chemical plants:
Fire, Explosions, Toxic Release.
• Organic solvents are the most common source
of fire & explosions.
• US lost $300M annually to such accidents.
• To prevent such accident, engineers must be
familiar
- Fire & explosion properties of materials
- Nature of fire & explosion process
- procedure to reduce fire & explosion
 The Fire Triangle
• Fuels:
• Oxidizers – Liquids
– Liquids • gasoline, acetone,
– Gases ether, pentane
• Oxygen, – Solids
fluorine, chlorine
• plastics, wood dust,
• hydrogen fibers, metal
peroxide, nitric
acid, perchloric particles
acid – Gases
– Solids • acetylene, propane,
• Metal peroxides, carbon monoxide,
ammonium hydrogen
nitrate  Ignition sources
 Sparks, flames, static
electricity, heat
 Principles of F & E preventions
• F & E will not occur if
1) Fuel is not present or is not in sufficient
quantity.
2) An oxidizer is not present or is not in
sufficient quantity.
3) The ignition source is not energetic
enough to initiate fire
Distinction between Fires and Explosions

- The major distinction fires and

explosions is the rate of energy release.

- Fires release energy slowly, while

explosions release energy very rapidly,
typically on the order of micro seconds.

- Fires can also result from explosions

and explosions can result from fires.
 Terminology

• Auto Ignition • Flash Point

Temperature • Ignition Energy
• BLEVE • Intermediate vapor
• Combustible Liquid pressure stocks
• Deflagration • VCE
• Detonation • Vapor Pressure
• Explosion
• Explosive Limits
• Fire
• Flammable Limits
• Flammable Liquids
 Definitions
• Fire
– Combustion or Fire is a chemical reaction in which
a substance combines with an oxidant and releases
energy

• Deflagration
– Propagating reactions in which the energy transfer
from the reaction zone to the unreacted zone is
accomplished thru ordinary transport processes
such as heat and mass transfer.

• Detonation / Explosion
– Propagating reactions in which energy is transferred
from the reaction zone to the unreacted zone on a
reactive shock wave. The velocity of the shock
wave always exceeds sonic velocity in the reactant.
 Detonation

• Highly turbulent combustion

• Very high flame speeds
• Extremely high pressures >>10 bars
 Flammability Limits (LFL and UFL)
Vapor – air mixtures will only ignite and burn over a well –
specified range of compositions.

The mixtures will not burn when the composition is lower

than the lower flammable limit (LFL), the mixture is too lean
for combustion.
The mixture is also not combustible when the composition
is too rich, that is, when it is above the upper flammable
limit (UFL).

A mixture is flammable only when the composition is

between the LFL and the UFL.

Commonly used units are volume percent fuel (percent of

fuel plus air).
Lower explosive limit (LEL) and upper explosive limit (UEL)
are used interchangeably with LFL and UFL.
Flammable Limits Change
With:

Inerts

Temperature

Pressure
Relationship between Various Flammability Properties
Flammability Characteristics of Liquids and
Vapors
Flammability characteristics of some important organic chemicals
(liquids and gases) are provided in table:
Flammability Characteristics of Liquids

The flash point (FP) is one of the major physical properties used to
determine the fire and explosion hazards of liquids.
Flash point for pure components is easily determined experimentally.
Flash Point Temperature Equation

Satyanarayana and Rao showed that the Flash point temperatures for
pure materials correlate well with the boiling point of the liquid.
They were able to fit the flash point for over 1200 compounds with an
error of less than 1% using the equation
 Vapor Mixtures Limits
Vapor mixtures limits are computed using the Le Chatelier equation
 Flammability Limit Depends on Temperature

The flammability range increases with temperature. The

following empirically derived equations are available for
vapors.
Flammability Limit Depends on Pressure

Pressure has little affect on the LFL except at very low

pressures (< 50 mm Hg absolute), where flames do not
propagate.
The UFL increases significantly as the pressure is increased,
broadening the flammability range.
An empirical expression for the UFL for vapors as a function
of pressure is available:
 Estimating Flammability Limits

For some situations it may be necessary to

estimate the flammability limits without
experimental data.

Jonnes found that for many hydrocarbon vapors

the LFL and UFL are a function of the
stoichiometric concentration (Cst) of fuel:

LFL = 0.55 Cst

UFL =3.50 Cst

Where Cst is volume % fuel in fuel plus air.

Correlation of the Flammability Limits

The stoichiometric concentration for most organic compounds is

determined using the general combustion reaction

CmHxOy + zO2 → mCO2 + x/2 H2O

Limiting Oxygen Concentration (LOC) and Inerting

The LFL is based on fuel in air.

Oxygen is the key ingredient and there is a minimum oxygen

concentration required to propagate a flame.

Explosions and fires are preventable by reducing the oxygen

concentration regardless of the concentration of the fuel.
Below the LOC, the reaction cannot generate enough energy to heat
the entire mixture of gases to the extent required for the self
propagation of the flame.

The LOC has units of percentage of moles of oxygen in total moles.

LOC is estimated either by using experimental data or by using the

stoicheometry of the combustion reaction and the LFL.
 What is MIE?

The minimum ignition energy (MIE) is the minimum energy

input required to initiate combustion.

All flammables (includes dust) have minimum ignition

energies.

The MIE depends on the specific chemical or mixture, the

concentration, pressure and temperature.

Experimental data shows that:

The MIE decreases with an increase in pressure

The MIE of dusts are, in general, at energy levels
comparable to combustible gases
An in the nitrogen concentration increases the MIE
 Ignition Energy
Many hydrocarbons have MIEs of about 0.25 mJ. This is
low compared with sources of ignition.

A few MIEs are given in table

 Auto-Oxidation
• The process of slow oxidation with accompanying
evolution of heat, sometimes leading to autoignition if
the energy is not removed from the system

• Liquids with relatively low volatility are particularly

susceptible to this problem

• Liquids with high volatility are less susceptible to

autoignition because they self-cool as a result of
evaporation

• Known as spontaneous combustion when a fire

results; e.g., oily rags in warm rooms; land fill fires
 Adiabatic Compression
• Fuel and air will ignite if the vapors are
compressed to an adiabatic temperature
that exceeds the autoignition temperature

• Adiabatic Compression Ignition (ACI)

• Diesel engines operate on this principle;

pre-ignition knocking in gasoline engines

• E.g., flammable vapors sucked into

compressors; aluminum portable oxygen
system fires
 Adiabatic Compression Equation

The adiabatic temperature rise for an ideal gas is computed

from the thermodynamic adiabatic compression equation
 Ignition Sources of Major Fires
Source Percent of Accidents
Electrical 23
Smoking 18
Friction 10
Overheated Materials 8
Hot Surfaces 7
Burner Flames 7
…
Cutting, Welding, Mech. Sparks 6
…
Static Sparks 1
All Other 20 33/61
 Explosions
Explosion behavior depends on a large number of
parameters
Explosion behavior is very difficult to characterize.
Should use extrapolated results cautiously and provide a
suitable “margin of safety” in all designs.
A summery of the more important parameters is shown in
table:
 Confined Explosions

A confined explosion occurs in a confined space, such as,

a vessel or a building.

The two most common confined explosion scenarios

involve explosive vapors and explosive dusts.

The nature of the explosion is a function of several

experimentally determined characteristics.

These characteristics are determined using two laboratory

devices:
- Test apparatus for acquiring vapor explosion data
- Test apparatus for acquiring dust explosion data
 Explosion apparatus for vapors

The test procedure includes:

Evacuating the vessel
Adjusting the temperature
Metering in the gases to obtain the proper mixture
Igniting the gas by a spark
Measuring the pressure as a function of time
 Explosion apparatus for dusts

The device is similar to the vapor explosion apparatus, with

the exception of a larger volume and the addition of a
sample container and a dust distribution ring.
The distribution ring insures proper mixing of the dust prior
to ignition.
 Explosion Characteristics

The explosion characteristics determined using the vapor

and dust explosion apparatus are used in the following
way:

1. The limits of flammability or explosivity are used to

determine the safe concentrations for operation or the
quantity of inert required to control the concentration within
safe regions.

2. The maximum rate pressure rise is indicative of the

robustness of an explosion. The explosive behavior of
different materials can be compared on a relative basis.
 Cubic Law

A plot of the log of the maximum pressure slope versus the

log of the vessel volume frequently produces a straight line
of slope -1/3 and this relationship is called “Cubic Law”.

• These equations are used to

estimate the consequence of an
explosion in a confined space
Blast Damage Resulting from Overpressure

Experiments with explosives have been demonstrated that the

overpressure can be estimated using an equivalent mass of TNT,
denoted mTNT, and the distance from the ground –zero point of the
explosion, denoted r.

The empirically derived scaling law is:

The equivalent energy of TNT is 1120 cal/g.

The scaled overpressure pS is given by

Where, pS is the scaled overpressure, p0 is the peak side on

overpressure and pa is the ambient pressure.
Damage Estimates for Common Structures Based
on Overpressure
Damage Estimates for Common Structures Based
on Overpressure
Correlation between scaled distance and explosion peak side-on
overpressure for a TNT explosion occurring on a flat surface.
TNT Equivalency

TNT equivalency is a simple method for equating a known energy of a

combustible fuel to an equivalent mass of TNT.

The approach is based on the assumption that an exploding fuel mass

behaves like exploding TNT on an equivalent energy basis.

The equivalent mass of TNT is estimated using the following equation:

Energy of Chemical Explosions

The blast wave resulting from a chemical explosion is generated by the

rapid expansion of gases at the explosion site.

This expansion can be caused by two mechanisms: 1. Thermal heating

of the reaction products 2. The change in the total number of moles by
reaction

The most hydrocarbon combustion explosions in the air the change in

the number of moles is small.

For example, consider the combustion of propane in air. The

stoichemetric equation is

C3H8 + 5O2 18.8N2 → 3CO2 + 4H2O + 18.8N2

Energy of Mechanical Explosions

For mechanical explosions a reaction does not occur and the energy is
obtained from the energy content of the confined substances.
Four methods are used to estimate the energy of explosion for a pressurized
gas:

Brode’s equation

Isentropic expansion

Isothermal expansion

Thermodynamic availability
 Vapor Cloud Explosions

The most dangerous and destructive explosions in the

chemical process industries are vapor cloud explosions
(VCE). These explosions occur by a sequence of steps:

1. Sudden release of a large quantity of flammable vapor.

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

2. Dispersion of the vapor throughout the plant site while

mixing with air.

3. Ignition of the resulting vapor cloud.

What happens to a vapor cloud

1. Cloud will spread from too rich, through flammable range to too lean
2. Edges start to burn through deflagration (Steady state combustion)
3. Cloud will disperse through natural convection
4. Flame velocity will increase with containment and turbulence
5. If velocity is high enough cloud will detonate
6. If cloud is small enough with little confinement it cannot explode.
 Prevention Methods of VCE

Methods which are used for preventing VCEs are:

1. Keeping low inventories of volatile/flammable
materials
2. Using process conditions which minimize
flashing if a vessel or pipeline is ruptured
3. Using analyzers to detect leaks at very low
concentrations
4. Installing automated block valves to shut
systems down while the spill is in the incipient
stage of development.
BLEVE Steps