04-05-2023

Chapter-10

Fire and Explosion

Introduction to Fires and Explosions

 The three most common chemical plant accidents are:
1) fires,
2) explosions, and
3) toxic releases.

 Chemicals present a substantial hazard in the form of

• fires and explosions.

 Organic solvents are the most common source of fires and explosions in the chemical
industry.

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Common Organic Solvents

 Acetic acid
 Acetone
 Benzene
 Carbon tetrachloride
 Chlorobenzene
 Chloroform
 Ethanol
 Methanol
 Toluene
• Etc.

 To prevent accidents resulting from fires and explosions, engineers must be familiar with:
• The fire and explosion properties of materials,
• The nature of the fire and explosion process, and
• Procedures to reduce fire and explosion hazards.

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Essential Elements for Fire

 The essential elements for combustion are:

1. fuel, (example: coal)
2. an oxidizer, (example: air or oxygen), and
3. an ignition source (example: matchbox or spark).
Coal

 These elements are illustrated by the fire triangle,

• shown in Figure -1 at next page).

Matchbox Air separation plant 5

The Fire Triangle

Fire :
1. Fuel When all sides
2. Air (Oxygen) are connected
3. Ignition source

Fire
Fire

Ignition sources

No Fire :
When any one Ignition source
side is missing

Figure-1: The fire triangle

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Fire or Burning
 Fire, or burning, is the rapid exothermic oxidation of an ignited fuel. Combustion or fire is a
chemical reaction in which a substance combines with an oxidant and releases energy. Part
of the energy released is used to sustain the reaction.

 The fuel can be in solid, liquid, or vapor form, but vapor and liquid fuels are generally easier
to ignite.

 The combustion always occurs in the vapor phase;

• liquids are volatized, and
• solids are decomposed into vapor before combustion.

 When fuel, oxidizer, and an ignition source are present at the necessary levels, burning will
occur.

 This means a fire will not occur if

1. fuel is not present or is not present in sufficient quantities,
2. an oxidizer is not present or is not present in sufficient quantities, and
3. the ignition source is not energetic enough to initiate the fire.

 Two common examples of the three components of the fire triangle are:
• wood, air, and a match-box; and
• gasoline, air, and a spark.
• diesel, air, and compression.
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FIRE
 However, other, less obvious combinations of chemicals can lead to fires and explosions.

 Various fuels, oxidizers, and ignition sources common in the chemical industry are:
• Fuels
 Liquids: gasoline, acetone, ether, pentane
 Solids: plastics, wood dust, fibers, metal particles
 Gases: acetylene, propane, carbon monoxide, hydrogen
• Oxidizers
 Gases: oxygen, fluorine, chlorine
 Liquids: hydrogen peroxide, nitric acid, perchloric acid (HClO4)
 Solids: metal peroxides, ammonium nitrite
• Ignition sources
 Sparks, flames, static electricity, heat.

Distinction between Fires and Explosions

 The major distinction between fires and explosions is the rate of energy release.

 Fires release energy slowly, whereas

• Explosions release energy rapidly,
 typically on the order of microseconds.

 Fires can also result from explosions, and

• Explosions can result from fires. Fire Explosion

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Example

 A good example of how the energy release rate affects the consequences of an
accident is a standard automobile tire.

 The compressed air within the tire contains energy, [Pressure energy].

 If the energy is released slowly through the nozzle, the tire is harmlessly deflated.

 If the tire ruptures suddenly and all the energy within the compressed tire
releases rapidly, the result is a dangerous explosion.

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Definitions
Table: Commonly used definitions related to fires and explosions
Item Description
Ignition Ignition of a flammable mixture may be caused by a flammable mixture
coming in contact with a source of ignition with sufficient energy or the gas
reaching a temperature high enough to cause the gas to auto-ignite.
Autoignition A fixed temperature above which adequate energy is available
temperature (AIT) in the environment to provide an ignition source.
Flash point (FP) Lowest temperature of a liquid at which it gives off enough vapor to form an
ignitable mixture with air
Fire point 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.

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Item Description
Flammability • Vapor-air mixtures will ignite and burn only over a well-specified range of
limits compositions.
• The mixture 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).
Explosion An explosion is a rapid expansion of gases resulting in a rapidly moving pressure
or shock wave.
Mechanical An explosion resulting from the sudden failure of a vessel containing high-
explosion pressure non-reactive gas
Confined • An explosion occurring within a vessel or a building. These are most common
explosion and usually result in injury to the building inhabitants and extensive damage.
• Most common confined explosion scenarios involve explosive vapors and
explosive dusts.

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Flammable Limits - Vapour Mixtures

 Defined in previous section, frequently LFLs and UFLs for mixtures are needed.
 Consider a mixture of combustible species
 The limits for vapours mixture are computed using the Le-Chatelier equation,
1
𝐿𝐹𝐿 =
𝑦
∑
𝐿𝐹𝐿
where, LFLi = Lower flammable limit for component i (in volume %) of component i in
fuel and air, yi = Mole fraction of component i on a combustible basis and n = Number
of combustible species.

 Similarly, 𝑈𝐹𝐿 =
∑

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where, UFLi = the upper flammable limit for component i (in volume %) of
component i in fuel and air.
 Le Chatelier's equation is empirically derived and is not universally applicable.
Mashuga and Crowl derived Le Chatelier's equation using thermodynamics.
 The derivation shows that the following assumptions are inherent in this equation:
• The product heat capacities are constant.
• The number of moles of gas is constant.
• The combustion kinetics of the pure species is independent and unchanged by
the presence of other combustible species.
• The adiabatic temperature rise at the flammability limit is the same for all
species.
 These assumptions were found to be reasonably valid at the LFL and less so at the
UFL. 15

Estimation of Flammability Limits

 Flammability limits are easily measured and experimental determination is

always recommended.
 For some situations, it may be necessary to estimate the flammability limits
without experimental data.
 For many hydrocarbon vapors the LFL and the UFL can be calculated from:
LFL = 0.55Cst ….(1) UFL = 3.5Cst ….(2)
where, Cst = Stoichiometric concentration = Volume % (mole %) of fuel in fuel plus
air
 Stoichiometric concentration for most organic compounds is determined as given
below.

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 Consider, general combustion reaction (For most organic compounds),

 O balance gives, y + 2z = 2m + x/2,

……(3)

 Now,

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 Cst

……(3)

 Putting value of z from equation 3,

𝐶 = ( )
.

 Putting value of Cst in equation 2 and 3,

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Limiting Oxygen Concentration and lnerting

 The Lower flammable limit (LFL) is based on fuel in air.

 Oxygen is the key ingredient and there is a minimum oxygen concentration

required to propagate a flame.

 This is an especially useful result, because explosions and fires can be prevented
by reducing the oxygen concentration regardless of the concentration of the fuel.

 Below the limiting oxygen concentration (LOC), the reaction cannot generate
enough energy to heat the entire mixture of gases (including the inert gases) to
the extent required for the self-propagation of the flame.
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 LOC is expressed in percentage of moles of oxygen in total moles.

 If experimental data are not available, the LOC is estimated using the
stoichiometry of the combustion reaction and LFL.

 LOC can be estimated using the equation, LOC = z(LFL)

where, z: O2 moles required per mole of fuel during combustion stoichiometry

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Adiabatic Compression

 Is known as an additional means of ignition

 For example, gasoline and air in an automobile cylinder will ignite if the vapors are
compressed to an adiabatic temperature that exceeds the auto-ignition temperature.

 Several large accidents have been caused by flammable vapors being sucked into the
intake of air compressors. Subsequent compression results in autoignition.

 The adiabatic temperature increase for an ideal gas is computed from the
thermodynamic adiabatic compression equation,

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Concepts to Prevent Fires and Explosions

 A threefold strategy is used to limit the potential damage from fires and explosions:
• Prevent flammable mixture,
• prevent the initiation of the fire or explosion, and
• minimize the damage after a fire or explosion has occurred.

 Methods to prevent/minimize fire and explosion:

• Inerting
• Purging
• Controlling static electricity,
• Ventilation,
• Use of explosion-proof equipment and instruments,
• Use of sprinkler systems, etc.
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Inerting

• A process of adding an inert gas to a combustible mixture to reduce the

concentration of oxygen below the limiting oxygen concentration (LOC).

• The inert gas is usually nitrogen or carbon dioxide, although steam is sometimes
used.

• For many gases the LOC is approximately 10%, and for many dusts it is
approximately 8%.

 Ideally this system should include an automatic inert gas addition feature to
control the oxygen concentration below the LOC.

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 This control system should have an analyzer to continuously monitor the oxygen
concentration in relationship to the LOC and a controlled inert gas feed system to
add inert gas when the oxygen concentration approaches the LOC.

 Several purging methods are used to initially reduce the oxygen concentration to
the lower than set point.

 Different Methods: Vacuum purging, pressure purging, combined pressure-

vacuum purging, vacuum and pressure purging with impure nitrogen, sweep-
through purging, and siphon purging

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Vacuum Purging
 Most common inerting procedure for vessels, not for large storage vessels

 Steps used in a vacuum purging

• Drawing a vacuum on the vessel until the desired vacuum is reached
• Relieving the vacuum with an inert gas, such as nitrogen or carbon dioxide, to
atmospheric pressure
• Repeating above steps until the desired oxidant concentration is reached.

 Consider a vessel of known size with an initial oxygen concentration yo and

pressure PH
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 The process for vacuum purging is clarified using

figure given.

 Vessel is vacuum-purged to a final target oxygen

concentration yj at pressure PL.

 Assuming ideal gas behavior, total moles at each

pressure,

n = n =

 Number of moles of oxidant at PL and PH,

(noxy)1L = y0nL, (noxy)1H = y0nH
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 When the vacuum is relieved with pure nitrogen, the moles of oxidant are the
same as in the vacuum state and the moles of nitrogen increase. The new oxidant
concentration after the first purge will be,
(noxy)1L n
𝑦 = = y0 L

 If the vacuum and inert relief process is repeated, the concentration after the
second purge will be,
(noxy)2L y1nL nL
𝑦 = = = y0

 This process is repeated as often as required to decrease the oxidant

concentration to a desired level.

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 So, oxidant concentration after j purge cycles, vacuum and relief, is given by,

nL
y = y0

This equation is helpful to find number of purge cycles (j) required to reduce oxygen
concentration from y0 to yj.

 Total moles of nitrogen added for each cycle is constant. So, the total nitrogen
added for j number of cycles,

∆𝑛 =𝑗 P −P

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Ventilation
 Proper ventilation is another method used to prevent fires and explosions.

 Purpose of ventilation: To dilute the explosive vapors with air to prevent explosion

 Open-air plants: Recommended because the average wind velocities are high enough to safely
dilute volatile chemical leaks that may exist within a plant.

 Plants Inside Buildings: Local and dilution ventilation systems are required.

 Local ventilation is the most effective method for controlling flammable gas releases.

 Mechanically or economically impossible to cover every potential release point with only local
ventilation, So, dilution ventilation is also used. 29

Sprinkler systems

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Sprinkler systems
 An effective way, consists of an array of sprinkler heads connected to a water supply

 The heads are mounted in a high location (usually near ceilings) and disperse a fine spray of
water over an area when activated.

 Wet pipe system:

• Activation of water heads individually by the melting of a fusible link holding a plug in the
head assembly.
• Once activated, the sprinklers cannot be turned off unless the main water supply is
stopped.
• Used for storage areas, laboratories, control rooms and small pilot areas.

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 Deluge system:
• Activation of entire sprinkler array from a common control point
• The control point is connected to an array of heat and/or smoke detectors that start the
sprinklers when an abnormal condition of fire is detected.
• Used for plant process areas and larger pilot plants

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Standards of Fire Extinguishers

 These fire extinguishers

are manufactured with

• ISO: 9001 standards

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Thanks

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