DCMH.

CH4051_Process Safety
Fire

Prepared by:

Dr. Mardhati Zainal Abidin

Universiti Teknologi PETRONAS

AP Ir. Dr. Risza Rusli

University of Doha for Science & Technology

For:
Ho Chi Minh City University of Technology

1
 Objectives

At the end of this chapter, students should be able to

• Understand the flammability characteristics of liquid, vapor and

gasses and the nature of fire
• Prevent fire by controlling ignition source, fuel concentration range
and oxygen content
• Estimate the impact of fire hazard

2
 Chapter Outline

• Hazardous material release & fire

• Fire triangle
• Flammability characteristics of liquids and vapours
• Flammability diagram
• Fire consequence

3
Consequences Analysis Procedure
Loss of containment
•Rupture or break in pipeline
Selection of a Release Incident •Hole in a tank or pipeline
•Runaway reaction
To describe release accident •Fire external to vessel
•Total quantity released
Selection of a Source Model
•Release duration
•Release rate Neutrally buoyant models
Results from the models
Selection of a Dispersion Model •Downwind concentration
•Area affected
•Duration

Models Flammable/Toxic
•TNT Equivalency
•Multi-Energy Explosion •Response vs dose
•Fireball •Probit model
Selection of Fire Selection of •Toxic response
Results
& Explosion Model Effect Model •No. of individuals affected
•Blast overpressure
•Radiant heat flux •Property damage
•Escape
•Emergency Response Mitigation Factors
•Containment dikes
•PPE

Consequence Model
4
 Hazardous Material Release
Hazardous materials are typically contained in storage or process vessels
(as a gas, liquid or solid).

Release of Solid Hazardous Material

The release is significant if the solid is:
• An unstable material such as an explosive
• Flammable or combustible solid (petroleum coke)
• Toxic or carcinogenic (either in bulk or as dust)
• Soluble in water and spill occurs over water (dissolves into the water)
• Dust (which can cause clouds and impact respiration)

Release of Liquids or Gases from Containment

Release from containment will result in:
• Instantaneous release if there is a major failure/rupture
• Continuous release if a hole develops in a vessel

5
 Hazardous Material Release

Consequences of Release from a Pressurised Storage Tank

Flammable Gas Release

No Ignition = vapour cloud (could be toxic)
Immediate ignition = jet fire
Delayed ignition = vapour cloud explosion

Flammable Liquid Release

No ignition = toxic health issues
Immediate Ignition – pool fire
Pool fire under or near a pressure vessel can lead to a Boiling
Liquid Expanding Vapour Explosion (BLEVE)

6
 Consequence - Fire

To prevent these accidents, need to be familiar with:

(1) Fire, explosion and toxicity properties of materials
(2) Nature of fire, explosion and toxic release process
(3) Procedures to reduce fire, explosion and toxic release hazards

Fire is the rapid exothermic oxidation of an ignited fuel.

Fuel may be in solid, liquid or vapour but combustion is always in the

vapour phase. Solids and liquids vaporize before combustion.

7
 Consequence - Fire

Event Type Event Mechanism Hazard Concern

Fires
Gas/Vapour - Jet fire, flash fire, fireball Thermal radiation, flame
Liquid - Pool fire, tank fire, running fire, spray impingement, combustion
fire, fireball products, initiation of
Solids - Bulk fire, smouldering fire further fires
Explosions
Confined - Runaway reactions, combustion Blast pressure waves,
explosion, physical explosion, missiles, windage,
boiling liquid expanding vapour thermal radiation,
Unconfined explosion (BLEVE) combustion products
- Vapour cloud explosion
Gas Clouds
Heavy - Jets Asphyxiation, toxicity,
Gases - Evaporation, volatilisation, boil-off flammability, range of
Light Gases concentrations.
8
 Consequence - Fire
TYPES OF FIRES
Jet Fires
• Occurs when a flammable liquid or gas is ignited after it is released
from a pressurized or punctured vessel or pipe.
• The pressure generates a long-flame which is stable under most
conditions
• For a two-phase jet, a part of the liquid may rain-out onto the floor
and give rise to pool fire.
• The duration of the fire is depends on the release rate and sources
capacity and the flame length is directly proportional to the flow rate.

9
 Consequence - Fire
TYPES OF FIRES
Jet Fires

10
 Consequence - Fire
TYPES OF FIRES
Jet Fires

11
 Consequence - Fire
TYPES OF FIRES
Pool Fires
• Occur on ignition of an accumulation of liquid as a pool on the
ground or on water or other liquid.
• A steady state burning is rapidly achieved as the flame vapor to
sustain the fire is provided by evaporation of the liquid by heat from
the flames.

12
 Consequence - Fire
TYPES OF FIRES
Pool Fires

13
 Consequence - Fire
TYPES OF FIRES
Flash Fire
• When a cloud of flammable gas and air is ignited.
• The speed of burning is a function of gas concentration and wind speed.
• The common example is fire due to gas leak and mistakenly ignited using
the cigarettes lighter.
• Damage is caused by thermal radiation and oxygen sudden depletion.
• Typical flame propagation is 4 m/s and increased with wind speed.
• Flash fire is transient (short period) in nature and the steady burning
period is even shorter and thus it is difficult to determine its emissive
powers and incipient fluxes.

14
 Fire Triangle

Fuels Oxidizers
• Liquids
• Liquids
- hydrogen
- gasoline, acetone,
peroxide, nitric
ether, pentane
acid,
• Solids
perchloric acid
- plastics, wood
• Gases
dust, fibers, metal
- oxygen,
particles
fluorine,
• Gases
chlorine
- acetylene,
Ignition • Solids
propane, carbon
monoxide, sources - metal
• Sparks, flames, peroxides,
hydrogen
static electricity, ammonium
heat nitrate
15
 Application of Fire Triangle

Fires and explosions can be prevented by removing any single leg from
the fire triangle.

Problem: Ignition sources are so plentiful that it is not a reliable control

method.

Robust Control: Prevent existence of flammable mixtures.

16
Flammability Characteristics of Liquids

• Flash Point Temperature : minimum

temperature at which a liquid gives off
sufficient vapour to form an ignitable
mixture with air near the surface of the
liquid.
• One of the major quantities used to
characterize fire and explosion hazard of
liquids.
• Determined in OPEN CUPS and CLOSED
CUPS test.
• Open cup values are higher than closed
cup values and apply to open vessels,
spills etc.
• Fire Point : the lowest temperature at
which a liquid will continue to burn,
normally slightly above the open cup flash
point. 17
Flammability Characteristics of Vapours
and Gases
• Flammable / Explosive Limits - Range of composition of material in air
which will burn
• Lower Flammability Limit (LFL) or Lower Explosive Limit (LEL)
- minimum concentration of a particular combustible gas or vapor
necessary to support its combustion in air
▪ Upper Flammability Limit (UFL) or Upper Explosive Limit (UEL)
- maximum fuel concentration through which a flame will propagate

• Normally expressed as volume percent fuel (% of fuel + air) at

atmospheric temperature and pressure

18
Flammability Characteristics of Vapours
and Gases
• The mixture will not burn when the composition is lower than the 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 UFL.
• A mixture is flammable only when the composition is between the LFL
and the UFL

19
Flammability Characteristics of Vapours
and Gases
• Auto Ignition Temperature (AIT)
• Temperature above which spontaneous combustion can occur
without the use of a spark or flame.
• The value depends on concentration of the vapor, material in
contact and size of the containment
• Minimum Oxygen Concentration (MOC)
• Oxygen concentration below which combustion is not possible.
• Expressed as volume % oxygen
• Also called Limiting Oxygen Concentration (LOC)
• Max. Safe Oxygen Conc. (MSOC)

20
Flammability Relationships
Saturation Vapor Pressure Curve

Vapor pressure / concentration

UFL

Flammable
Liquid
Auto-ignition zone
Gas

LFL

Flash Point AIT: Auto Ignition Temp

Temperature → Ambient Temperature
 Typical Values
LFL UFL
Methane: 5% 15%
Propane: 2.1% 9.5%
Butane: 1.6% 8.4%
Hydrogen: 4.0% 75%

Flash Point Temp. (deg F)

Methanol: 54
Benzene: 12
Gasoline: - 40

AIT (deg. F) MOC (Vol. % O2)

Methane: 1000 Methane: 12%
Methanol: 867 Ethane: 11%
Toluene: 997 Hydrogen: 5%
 Flammability Limits of Mixtures

LFLi is the lower flammable limit for component i (in vol %) of component i
in fuel and air.
yi is the mole fraction of component i on a combustible basis, and
n is the number of combustible species.

Assumptions:
1) Product heat capacities constant
2) No. of moles of gas constant
3) Combustion kinetics of pure species unchanged
4) Adiabatic temperature rise at the flammability limit is the same for all
species. 23
Example - Flammability Limits of Mixtures

Question:
What are the LFL and UFL of a gas mixture composed of 0.8% hexane, 2.0%
methane, and 0.5% ethylene by volume?

24
Example - Flammability Limits of Mixtures
Answer:
The mole fractions on a fuel-only basis are calculated in the following table.

25
 Limiting Oxygen Concentration (LOC)

• There is a minimum oxygen concentration required to propagate a

flame.
• Explosions and fires can be prevented by reducing the oxygen
concentration regardless of the concentration of the fuel.
• This procedure is known as inerting.
• LOC is also known as minimum oxygen concentration (MOC)
• The LOC depends on the inert gas species and has units of
percentage of moles of oxygen in total moles.
• If experimental data are not available, the LOC can be estimated
using stoichiometry of the combustion reaction and the LFL.

26
Limiting Oxygen Concentration (LOC)

LFL is based on fuel in air. Oxygen is the key ingredient for

fire/explosion. There must be a minimum O2 concentration (MOC or
LOC) required to propagate the flame

Example
Estimate the LOC for butane. LFL for butane is 1.9% vol.

Stoichiometry for this reaction:

C4H10 + 6.5O2 4CO2 + 5H2O

LOC = (Moles fuel/total moles) x (moles O2/moles fuel)

= LFL x (moles O2/moles fuel)
= 1.9 x (6.5 moles O2/1.0 moles fuel)
= 12.4 vol.% O2

27
Limiting Oxygen Concentration (LOC)

28
Flammability Diagram

29
 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.

Flammability diagram can be approximated.

30
 Flammability Diagram

1) Draw LFL and UFL on air line (%Fuel in air).

2) Draw stoichiometric line using z from combustion reaction.
3) Plot intersection of LOC with stoichiometric line.
4) Draw LOL and UOL in pure oxygen, if known (% fuel in pure
oxygen).
5) Connect the dots to get approximate diagram.
 Example
Methane:
LFL: 5.0% fuel in air (Appendix G)
UFL: 15% fuel in air (Appendix G)
LOC: 12% oxygen (Table 6-3)
Combustion Reaction: CH4 + 2 O2 --> CO2 + 2 H2O ; z = 2

Pure Oxygen: (Table 6-2)

LOL: 5.1% fuel in oxygen
UOL: 61% fuel in oxygen
 Flammability Diagram

Step 1: Draw LFL and UFL

on air line (%Fuel in air).
0 100
Air Line, all
Air line always extends combinations of fuel +
air
FROM: Fuel: 0%, Oxygen:
21% Nitrogen: 79%

TO: Fuel: 100%, Oxygen:

0%, Nitrogen: 0% Flammable
100
0
0 100
Nitrogen
 Flammability Diagram

Step 2: Draw LFL & UFL 0 100

line Air Line, all
combinations of fuel +
Identify LFL & UFL value air
from database

LFL & UFL line always

UFL (15%)
extends
100 LFL (15%)
FROM: Fuel axis 0
0 100
TO: Air line Nitrogen
 Flammability Diagram

Step 3: Draw stoichiometric line using z

from combustion reaction. 0 100
Air Line, all
Fuel + (z) Oxygen ---> Products
combinations
CH4 + 2 O2 --> CO2 + 2 H2O of fuel + air

z =z 2 
  *100 = 66.7%
 1+ z  66.7% UFL (15%)

100 LFL (15%)

FROM: Fuel: 0%, Oxygen: 100% 0
0 100
Nitrogen: 100% Nitrogen

TO: Oxygen: 66.7%

 Flammability Diagram

0 100
LOC (12%) Air Line, all
Step 4: Draw the LOC line
combinations
Identify LOC value from of fuel + air
database

Draw parallel line with fuel line 66.7% UFL (15%)

from LOC value
100 LFL (15%)
0
0 100
Nitrogen
 Flammability Diagram

Step 5: Draw LOL and UOL in pure oxygen, if known (% fuel in pure
oxygen). Connect the dots to get approximate diagram.

0 100
LOC = 12% oxygen

61% Methane

66.7%
O2 UFL = 15% fuel
100 LFL = 5.3% fuel
0 0
Nitrogen 100
5.1% Methane
 Flammability Zone
0 100
Apparatus pressure
Flammabl
limit
e
Non-
Flammable 20 80

40 60

60 40

80 20

100 0
0 20 40 60 80 100

Nitrogen
 Flammability Zone
0 100
Apparatus pressure limit
Flammable
Non-Flammable
20 80

40 60

60 40

80 20

100 0
0 20 40 60 80 100

Nitrogen
 Consequence Model – Hazard Levels or Effects
(Thermal Radiation Hazard)
FIRE HAZARD TO PLANT

Radiation Protection can be achieved by:

• Radiation is a function of emissivity of the • Elimination or segregation of
flame, the distance from the flame to the combustible materials
target surface, effective fire area, the view
factor, absorptivity, atmospheric • Use of incombustible materials for
transmittance and the fraction of the construction and insulation of
combustion energy radiated. vessels
• A tank, which is adjacent to another, can • Control of ignition sources
fail due to the following: • Stringent operational procedures
1. Heat input raising the product surface • Automatic detection and
temperature above its flash point extinguish of fire
2. A flammable mixture reaching a source • Incombustible and durable
of ignition or vice versa insulation for steel structure
3. Over temperature damage to the tank • Compliance to international code
shell or roof leading to the tank failure of fire protection and fire fighting
Consequence Model – Hazard Levels or Effects
(Thermal Radiation Hazard)
 Consequence Model – Hazard Levels or Effects
(Thermal Radiation Hazard)
• Hazard effects can be caused by the release of hazardous material
• Hazard level at receptor points shall be estimated for an accident to
measure the severity of the consequence due to the exposure to the hazard.
• Modelling Major Fire - Example
 Consequence Model – Hazard Levels or Effects
(Thermal Radiation Hazard)


• The variable responsible for the fire growth hazard is the mass burning rate, m

(kg/s). Other related extensive variables are energy/heat release rate, Q(kJ/s)
and the heat of combustion, ∆HC (kJ/kg).

 = m H (kJ/s)
• The total heat release by hydrocarbon is obtained via: Q C

A
• The burning rate can be decomposed into the burning rate per unit area , m
(kg/s·m2) and the surface area, A (m2).
m = m A A
• The main concern is the exposure to thermal radiation which could be
quantified as Q r = F Q
where F = proportion of heat transferred by radiation
(typically about 0.2)
 Example
Hazard Levels or Effects – Pool Fire

The reactor product is gasoline and the reactor is surrounded by a circular

bund of 10 m diameter. The runaway reaction leads to a gasoline leak which
then occupies the bunded area. Given that the gasoline ignites, determine:

i. The total radiative flux from the flame

ii. The incident thermal radiation on persons standing 15 m from the
circumference of the bund.

Assume the wind speed is negligible, the proportion of heat radiated is 0.4,
the mass burning rate per unit area is 0.1 kgm-2s-1 , the density of air at
ambient temperature is 1.17 kg m-3, the calorific value of the fuel is 45 MJ kg-1
and the atmospheric transmissivity is 1.0.
 Example
Hazard Levels or Effects – Pool Fire

The mass burning rate is

 kg    10 m 2  kg
m = m A A =  0.1 2  x   = 7.85
 m s  4  s

Total energy released

Q = m H C =  7.85 kg 2  x  45 x 106 J  = 3.53 x 108 W

 s   kg 

Total radiative energy from flame

Q r = F Q = 0.4 x 3.53 x 108 = 1.4 x 108 W

 Example
Hazard Levels or Effects – Pool Fire
0.61
Flame height 𝑚ሶ 𝐴
𝐻𝐹 = 𝐷𝐹 ∗ 42 0.5
𝜌𝑎𝑖𝑟 𝑔 𝐷𝐹
0.61
0.1 kgΤm2 s
= 10 m x 42 x
kgൗ
1.17 3 x 9.81 mΤs ⋅ 10 m 0.5
m
= 23 m
The incident thermal radiation at 15 m from the bund edge
where S2 = (202 +11.52) = 532 m2

𝜏 𝐹 𝑄ሶ 1 x 1.4 x 108
𝐼= 2
=
4𝜋𝑆 4 𝜋 𝑆2
1 x 1.4 x 108 W
𝐼= = 21000 2 Sm
4 𝜋 (532) m
(HF/2) m
(D/2 + 15) m
 Example
Hazard Levels or Effects – Pool Fire