Kathmandu University

Chemical Process Safety

Fire and Explosion

Dr. Ziaul Haque Ansari

Department of
Chemical Science and Engineering
Chemical Industries

Chemicals have become a part of our life for sustaining many

of our day-to-day activities, preventing and controlling
diseases, and increasing agricultural productivity etc.

An estimation of one thousand new chemicals enter the

market every year, and about 100,000 chemical substances are
used on a global scale. These chemicals are mostly found as
mixtures in commercial products. Over one million such
products or trade names are available.
Chemical Industries

The chemical industrial sector includes, organic, inorganic

chemicals, dyestuffs, paints, pesticides, specialty chemicals, etc.

The risks associated with the chemical industry are

commensurate with their rapid growth and development.

Apart from their utility, chemicals have their own inherent

properties and hazards.

Some of them can be flammable, explosive, toxic or corrosive

etc, and also have the potential to affect the nearby environment.
Safety Concern

For any industry to be successful, it is essential to inculcate

safety culture, consciousness in health and environment aspects in
each personnel of an organisation.

The significance of Safety & Health in chemical industries has

been a vital issue in achieving productivity and an edge in the
competitive world.
Hazard & Safety
Can cause:

Injury
Death
Damage to equipment/property

Practically impossible to completely eliminate all hazards.

Safety = freedom from hazards

Maintain a safe work environment

Control unsafe acts and conditions

Ensure operational efficiency

Work Place Hazard

Physical Hazards:
falling objects, slips & trips, dangerous machinery,..

Chemical Hazard
solvents, metals,..

Biological Hazard
micro-organisms and toxins

Psychosocial issues
ergonomics (design of work place environment)
work stress, violence,
 Major Concern in a Chemical Industry
1.Dangerous Materials : explosives, gases, flammable liquids/solids,
oxidizing substances, miscellaneous dangerous substances

2.Flammable : gases, vapours and dust

3.Hazardous : chemical reactions, pressure vessels, instrument

failures, unit operations, corrosion

4.Confined Spaces

5.Plant Alteration and Modification

DSEAR : Dangerous Substances and Explosive Atmospheres Regulations, 2002 (UK)

A set of regulations concerned with protection against risks from fire, explosion
and similar events arising from dangerous substances used or present in the workplace.
 Fire

In order to have a fire, two components are required fuel and an

oxidant.

for e.g. CH4 + 2O2 → CO2 + 2H2O

However, the presence of fuel and oxidant is not sufficient to start

combustion; the mixture must be raised to a high enough temperature
to start the reaction, usually by a spark or a flame.
The Fire Triangle
Oxidizers
Liquids: hydrogen peroxide, nitric Ignition sources
acid, perchloric acid sparks, flames,
Solids: metal peroxides, ammonium static electricity, heat
nitrate
Gases: oxygen, fluorine, chlorine

Fuels
Liquids: gasoline, acetone, ether, pentane
Solids: metal particles, wood dust, fibers, plastics,
Gases: acetylene, propane, hydrogen
 Fire

A 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.

 Fire or burning, is the rapid exothermic oxidation of an ignited

fuel.
 When fuel, oxidizer, and an ignition source are present at the
necessary levels, burning will occur.
 Source of Ignition

Open flames: this varies from a lit cigarette to welding activity.

Mechanically generated impact sparks: a hammer blow on a rusty

steel surface compared to a hammer blow on a flint stone.

Electric sparks: a bad electrical connection or a faulty pressure

transmitter.
Source of Ignition

High surface temperature: be the result of milling, grinding,

rubbing, mechanical friction in a stuffing box or bearing, or a
hot liquid pumped into a vessel.

Electrostatic discharge: Static electricity can be generated by air

sliding over a wing.

Adiabatic compression: Air is pumped into a vessel and the

vessel surface heats up.

Radiation, Lightning strikes.

Fire

In the past the sole method for controlling fires and explosions was
elimination of or reduction in ignition sources.

Practical experience has shown that this is not robust enough - the
ignition energies for most flammable materials are too low and
ignition sources too plentiful.

As a result, current practice is to prevent fires and explosions by

continuing to eliminate ignition sources while focusing efforts
strongly on preventing flammable mixtures.
Fire

Flash point (FP):The flash point of a liquid is the lowest

temperature at which it gives off enough vapor to form an ignitable
mixture with air.
At the flash point the vapor will burn but only briefly.

Fire point: The fire point is the lowest temperature at which a vapor
above a liquid will continue to burn once ignited.
The fire point temperature is higher than the flash point.
Flammability/Explosive Limit
For each flammable chemical we can determine limits,
concentration
of gas or vapor in air that are at the low or high extremes of ability
to
sustain continuous combustion.

There is a lower flammability limit (combustion-lean

limit mixture), a concentration in air, usually
expressed as volume percent (vol%), below which
the fuel-air mixture dose not sustain continuous
combustion.

*Upper Explosive Limit

*Lower Explosive Limit
Flammability/Explosive Limit
The Upper flammability limit (combustible-rich limit mixture) is
the highest concentration of fuel in air that burns continuously.

Such values should not be treated as absolute

physical constant such as melting point or density
of a pure substance, but rather as guidelines when
establishing criteria for safe conditions.

flammability limits vary with temperature, pressure,

and conditions of combustion.

*Upper Explosive Limit

*Lower Explosive Limit
Fire
Fire

 Figure is a plot of concentration versus temperature and shows

how several of these definitions are related.

 The exponential curve in Figure represents the saturation vapor

pressure curve for the liquid material.

 Typically, the UFL increases and the LFL decreases with

temperature.
Fire
 The LFL theoretically intersects the saturation vapor pressure
curve at the flash point, although experimental data do not always
agree with this.

 The autoignition temperature is actually the lowest temperature of

an autoignition region.

 The behavior of the autoignition region and the flammability

limits at higher temperatures are not known.

 The flash point and flammability limits are not fundamental

properties but are defined only by the specific experimental
apparatus and procedure used.
 Autoignition Temperature

The autoignition temperature of a

substance is the lowest temperature at
which it will spontaneously ignite without
an external source of ignition.

This temperature is required to supply the

activation energy needed for combustion.

The temperature at which a chemical will

ignite decreases as the pressure increases
or oxygen concentration increases. It is
usually applied to a combustible fuel
mixture.
Flammability limit for Hydrocarbons
Explosion
Fire and explosion may be two sides of the same coin
where both are based on a strongly exothermic (heat-
producing) chemical reaction, usually combustion in air.

Explosion occurs when the rapid expansion of gases produces

high pressures.

Rapid progression of high pressure and heat result in

explosion.

An explosion is more likely when the fuel-oxygen mixture is

midway between the flammability limits
Distinction between Fire and Explosion

The major distinction between fires and explosions is the

rate of energy release.

Fires release energy slowly, whereas explosion release

energy rapidly, typically on the order of microseconds.

Fires can also result from explosions, and explosions can

result from fires.
Distinction between Fire and Explosion

Example : an automobile tyre

The compressed air within the tyre contains energy. If the

energy is released slowly through the nozzle, the tyre is
harmlessly deflated.

If the tyre ruptures suddenly and all the energy within the
compressed tire release rapidly, the result is a dangerous
explosion.
Explosion
BLEVE (Boiling Liquid Expanding Vapor Explosion):
This is a type of explosion that can occur when a vessel
containing a pressurized liquid is ruptured.
Such explosions can be extremely hazardous.

Vapor cloud explosion: Overpressure caused when a gas

cloud detonates or deflagrates in open air rather than simply
burn, i.e. extremely rapid flame front propagation.

Detonation and Deflagration

Explosion
Deflagration: An explosion in which the reaction front moves at
subsonic speed (speed less than the speed of sound) in the unreacted
medium. Flame propagation velocity, typically far below 100 m/s,
and relatively modest overpressures, <0.5 bar.

Detonation: An explosion in which the reaction front moves at

supersonic speed (speed greater than the speed of sound) in the
unreacted medium. Flame propagation velocities, up to 2000 m/s, and
substantial overpressures, up to 20 bars.
Explosion
Confined explosion: An explosion occurring within a vessel or
a building. These are most common and usually result in injury
to the building inhabitants and extensive damage.

Unconfined explosion: Unconfined explosions occur in the

open. This type of explosion is usually the result of a flammable
gas spill. The gas is dispersed and mixed with air until it comes
in contact with an ignition source.

Unconfined explosions are rarer than confined explosions

because the explosive material is frequently diluted below the
LFL by wind dispersion.
Experimental Determination - Flashpoint
Flash point determination
When a temperature is reached at which the liquid is volatile
enough to produce a flammable vapor, and a momentary
flashing flame occurs.

The temperature at which this first occurs is called the flash

point temperature.

Note that at the flash point temperature only momentary

flame occurs; a higher temperature, called the fire point
temperature, is required to produce a continuous flame.
Examples of flash points
Gasoline (petrol) is designed for use in an engine which
is driven by a spark.

The fuel should be premixed

with air within its flammable
limits and heated above its flash
point, then ignited by the spark plug.

The fuel should not preignite in the hot engine.

Therefore, gasoline is required to have a low flash point
and a high autoignition temperature.
Theoretical flash point
Mathematically flash point can be calculated using boiling
point relationship:

where, Tf is flash point in K,

a, b, and c are constants,
Tb is boiling point in K
Constants for Tf equation
Constants used in the equation for predicting flash point
Flammability Limit Dependence on Temperature

Temperature dependencies

Where ΔHc is the net heat of combustion (kcal/mole), and T is temperature in C

As temperature increses, UFL increases, LFL decreases

Flammability range increases

Pressure dependencies

where P is absolute pressure in Mega Pascal

As pressure increases, UFL increases

Pressure has little effect on LFL
Example : Pressure dependencies
Estimating Flammability Limits
For some situations it may be necessary to estimate the
flammability limits without experimental data.

Using stoichiometric balance for general combustion reaction

where z has units of moles O2/mole fuel.

For many hydrocarbon vapors the LFL and the UFL are a function
of the stoichiometric concentration (Cst) [vol%] of fuel:

Approximate LFL = 0.55 Cst

UFL = 3.50 Cst
Estimating Flammability Limits
Estimating Flammability Limits
Example : Estimate the LFL and the UFL for hexane, and compare
the calculated limits to the actual values determined experimentally.

Solution
The stoichiometry is

LFL = 0.55(100)/[4.76(6) + 1.19(14) + 1]

= 1.19 vol. % versus 1.2 vol. % actual,
UFL = 3.5(100)/[4.76(6) + 1.19(14) + 1]
= 7.57 vol. % versus 7.5 vol. % actual.
Calculating LFL/UFL of Mixtures
Frequently LFLs and UFLs for mixtures are needed. These
mixture limits are computed using the Le Chatelier
equation

Where,
LFLi and UFLi are the lower and upper flammable limits for
component i (in volume %) of component i in fuel and air,
yi is the mole fraction of component i on a combustible basis,
n is the number of combustible species
 Calculating LFL/UFL of Mixtures
Example : What are the LFL and UFL of a gas mixture composed of
0.8% hexane, 2.0% methane, and 0.5%
ethylene by volume?

Solution
Limiting Oxygen Conc. (LOC)
There is a minimum oxygen concentration required to
propagate a flame.
Flammability Diagram
A general way to represent the flammability of a gas or
vapour is by the triangle diagram as shown in the figure
below.

Concentration of fuel,
oxygen and inert material are
plotted on the three axes.

Each apex of the triangle

represents either 100% fuel,
oxygen or nitrogen.
How to draw a Flammability diagram?
Draw LFL and UFL on air line (% fuel in air)

Locate stoichiometric point on the oxygen axis

Draw stoichiometric line from this point to 100% nitrogen apex

Locate LOC on the oxygen axis and draw line parallel to the fuel
axis until it intersects the stoichiometric line. Draw a point at the
intersection.

Draw LFL and UFL in pure oxygen if known (% of fuel in pure

oxygen)

Connect the points to get the flammability diagram

Flammability Diagram
Air line represents all possible combinations of fuel plus air. The
air line extends from point where fuel is 0% to oxygen 21% and
nitrogen is 79% to a point where fuel is 100%, oxygen 0% and
nitrogen 0%. The equation for this line is
Fuel% = -(100/79) x N2% + 100

Stoichiometric line represents all stoichiometric combinations of

fuel & oxygen
Fuel + zO2 = combustion products
where z is the stoichiometric coefficient for oxygen
Flammability Diagram
1.Draw Air Line
2. Enter LFL & UFL
3. Determine z
4. LOC = z LFL
5. Add Stoichiometric Line
6. Get Pure Oxygen LFL and
UFL (if available)
7. Construct curve
Example: Methane
Flammability Characteristics of Methane
Flammability limit in Air LFL 5.3 % fuel in air
UFL 15 % fuel in air
Flammability limit in pure LFL 5.1 % fuel in Oxygen
Oxygen UFL 61 % fuel in Oxygen
LOC 12 % Oxygen

Combustion reaction in our case will be

Now z=2, by comparing our case with the standard equation for combustion

Stoichiometric point = [z/(1+z)]*100= 66.7% of oxygen

The End