Chemical Process Safety

Chapter 6: Fires & Explosions

 Learning Objectives:
Chapter 6: Fires and Explosions
1. Describe the nature of fires and explosions.
2. Define the fire triangle and explain how to use it
to prevent flammable mixtures.
3. Characterize the flammability of gases, liquids,
and dusts.
4. Estimate flammability parameters for mixtures.
5. Draw a flammability triangle diagram and apply it.
6. Describe explosions and how to estimate
damage.

2
Case History
Case History
 Accident Statistics
Evaluation of the largest chemical plant accidents:

Explosions: 30%

Other:
3%
Fire
31%
Vapor
cloud explosion
36%

Most of the large accidents are due to fires and

explosions.
 Introduction
FIRE rapid exothermic oxidation, with flame
EXPLOSION higher energy release rate (mixture) } may trigger
each other
pressure or shock wave

EFFECTS Thermal radiation,

asphyxiation, toxic products,
blast wave, fragments,
} injuries / casualties
property losses
process interruption
building collapse

REQUIRED KNOWLEDGE FOR PREVENTION

material properties
nature of fire and explosion process
procedures to reduce hazards (Ch. 7)
 Fire Triangle

FIRE TRIANGLE FUEL

OXIDIZER
IGNITION SOURCE

Fu
t
an
Figure 6-1

el
id
Ox
Ignition Source

Oxidant may not be oxygen, e.g., chlorine.

 Fire Triangle
FUELS Gases Acetylene, Propane, CO, H2
Liquids * Gasoline, Organic Solvents
Solids * Plastics, Wood Dust, Fibers, Metal Particles

OXIDIZERS Gases: O2 , F2 , Cl2

Liquids: H2O2 , HNO3 , HCl3O
Solids: Peroxides, NH4 , NO2

IGNITION
SOURCE

* Liquids are volatized and solids decomposed prior to their

combustion in the vapor phase

Sufficient quantity / energy required.

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

Problem: Ignition
sources are so plentiful

Fu
t
an

el
id
that it is not a reliable

Ox
control method. No
Fire

Ignition Source

Robust Control: Prevent flammable mixtures

Combustion Behavior – Most Hydrocarbons

Smoke and fire are very visible!

Slide courtesy of Reed Welker.
 Combustion Behavior – Carbon Disulfide

No smoke and fire, but heat release rate just as

high.
Slide courtesy of Reed Welker.
 Combustion Behavior – Methane

Methane burns mostly within vessel, flame

shoots out of vessel.
 Combustion Behavior – Dusts

Much of the dust burns outside of the

chamber.
 Definitions - 1
LFL (LEL): Lower Flammability (explosion) Limit
Below LFL, mixture will not burn, it is too lean.
UFL (UEL): Upper Flammability (explosion) Limit
Above UFL, mixture will not burn, it is too rich.

Defined only for gas mixtures in air.

UNITS: Vol% fuel in air
 Definitions - 2
Flash Point: Temperature above which a liquid produces
enough vapor to form an ignitable mixture
with air.
Defined only for liquids at 1 atm. pressure.
Auto-Ignition Temperature (AIT): Temperature above
which adequate energy is available in the
environment to provide an ignition source.

Both terms apply to liquids.

 Definitions - 3

Limiting Oxygen Concentration (LOC): Oxygen

concentration below which combustion is not
possible, with any fuel mixture.
Expressed as volume % oxygen.
Primary design criteria for prevention.

Also called: Minimum Oxygen Concentration

Max. Safe Oxygen Conc.
Others
 Typical Values - 1
LFL UFL
Methane: 5.3% 15%
Propane: 2.2% 9.5% See Appendix B
Butane: 1.9% 8.5%
Hydrogen: 4.0% 75%

Flash Point Temp. (deg C)

Methanol: 12.2
Benzene: -11.1
Gasoline: -43
 Typical Values - 2
AIT (deg. C) Appendix B
Methane: 632
Great variability in
Methanol: 574
reported AIT values!
Toluene: 810 Use lowest value.

LOC (Vol. % Oxygen)

Methane: 12%
Table 6-2
Ethane: 11%
Hydrogen: 5%
 Flammability Relationships
Vapor pressure curve
Vapor pressure / concentration

UFL
UFL
Flammable
Liquid Auto-ignition zone
Gas
LFL
LFL

Flash Point AIT

Ambient Temperature
Figure 6-2 Temperature
 Minimum Ignition Energies

What: Energy required to ignite a flammable mixture.

Typical Values: (wide variation expected)
Vapors: ~ 0.2 mJ
Dusts: ~ 10 mJ
Dependent on test device --> not a reliable design
parameter.
Static spark that you can feel: about 20 mJ
Table 6-4
 Experimental Determination - LFL, UFL

Run experiment at different fuel compositions with

air: 10
Pressure (bar-gauge)

8
Maximum Explosion

Need a criteria to
define limit - use 1
6
psia pressure
increase. Other
4
criteria are used -
with different
2
results!
LFL UFL
0
0 2 4 6 8 10

See Figure 6-5

Fuel Concentration in air
(vol%)
Flammability limits are an empirical artifact of
experiment!
 Flammability Limit Behavior -1

As temperature increases:
UFL increases, LFL decreases
--> Flammability range increases
0.75 100CP
LFLT = LFL25 - (T - 25) = LFL25 - (T - 25)
DH c DH c
0.75
UFLT = UFL25 + (T - 25) Equations 6-4, 6-5
DH c
o
Approx. for many
T: C hydrocarbons
DH c : kcal/mole, heat of combustion
 Flammability Limit Behavior -2

As pressure increases:
UFL increases
LFL mostly unaffected

UFLP = UFL + 20.6 * (logP + 1)

P is pressure in mega-Pascals, absolute
No theoretical basis for this!

Pressure and temperature effects on flammability

limits is poorly understood – estimation methods
are poor.
 Flammability Limits of Mixtures
Le Chatelier Rule (1891)

1 1
LFLmix = n UFLmix =
yi n
yi
å
i =1 LFLi
å
i =1 UFLi

yi on a combustible basis only

Assumptions: 1) Product heat capacities constant

2) No. of moles of gas is constant
3) Combustion kinetics of pure species unchanged
4) Adiabatic temperature rise the same for all species

Details provided in Process Safety Progress, Summer 2000.

 Flammability Limits - Le Chatelier

LeChatelier’s rule shows that the LFL can be approximated by:

æ LFL ö C p DT *
ç ÷@
è 100 ø ( -Dhc )
Where Cp is the product heat capacity, DT is the adiabatic
*

temperature rise, and Dhc is the heat of combustion.

1200 K is frequently used as the adiabatic temperature rise at
the flammability limit.
A similar expressions is written for the UFL.
 Adiabatic Temperature Rise:

nFuel (-DhComb ) nFuel (-DhComb ) yFuel (-DhComb )

DT = Prods
@ @
nProdsC p nTotalC p Cp
CP DT*
æ LFL ö
y Fuel = =ç ÷
( -DhComb ) è 100 ø
1200 K is frequently used as the adiabatic
temperature rise at the flammability limit.
A similar expression is written for the UFL.
 Flammability Limits of Mixtures

æ LFL ö C p DT
*

ç ÷@
è 100 ø ( -Dhc )

From this equation, a plot of the flammability limit

vs. 1/(Heat of Combustion) should yield a straight
line if Le Chatelier’s rule is valid.

If this is done, one finds that:

Le Chatelier’s rule works better at the lower
flammability limit than the upper flammability
limit.
Assumptions are more valid at LFL.
 Lower Flammability Limit and Heat of Combustion

8.0
LFLN Comp. = 5327.4[1/D hc ]
7.0 R2 = 0.9478
LFL [Vol% Fuel in air]

LFLHC Comp. = 4569.1[1/D hc ]

6.0 R2 = 0.8849

5.0 LFLOxy. Comp. = 5030.7[1/D hc ]

R2 = 0.9338
4.0 Hydrocarbons
3.0 Oxygen Compounds
2.0
Nitrogen Compounds
1.0
Sulfur Compounds
0.0
0.0000 0.0002 0.0004 0.0006 0.0008 Linear (Nitrogen
0.0010 0.0012 0.0014
Compounds)
1/D hc [kJ/mole]-1 Linear (Hydrocarbons)

Linear (Oxygen
Compounds)
 Upper Flammability Limit and Heat of
Combustion
100
UFL [vol. % fuel in air]

80

60

40 Hydrocarbons
Oxygen Compounds
Nitrogen Compounds
20
Sulfur Compounds

0
0.000 0.001 0.001 0.002 0.002
-1
1/(-D hc) [kJ/mol]
 Estimating Flammability
Estimating flammability limits for hydrocarbons JONES(1928)

LFL = 0.55 × Cst Cst fuel stoichiometric conc. [vol%]

UFL = 35
. × Cst Equations (6-7), (6-8)

General combustion reaction:

x
Cm H x O y + zO 2 ® mCO 2 + H 2 O
2
z=m+¼x-½y

Cst = 21% In Air

0.21+z 31
 Estimating LOC
LOC: limiting oxygen conc. [vol% O2]
(1)Fuel + (z) Oxygen --> Products

Typically 8 - 10%

LOC = LFL x (moles of O2/moles of fuel)

This is very approximate and

is not always conservative!

32
 Flashpoints of Liquid Mixtures
Rule: At flashpoint temperature of mixture, the
partial pressure of the flammable is equal to the
saturation vapor pressure of the pure component at
its flash point.

Pure Mix

Psat = 100 mm Hg Partial pressure of

at flashpoint of flammable =
pure at mixture flashpoint

When possible, get data as close to process conditions.

Use only for mixtures with one flammable 33
Flammability Diagram
Upper limit in 100
pure oxygen
Air Line
Flammability 20 80
Zone en A

40 60

Fu
yg

el
Ox

60 40
Lower limit in Stoic
hiom
pure oxygen etric
80 lin e UFL 20

MOC
100 LFL 0
0 20 40 60 80 100

Nitrogen
34
 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.

35
 Flammability Diagram - 1
(1) Fuel + (z) Oxygen ---> Products
0 100
60% Fuel,
25% 25% Oxygen,
15% Nitrogen
en

Fu
60%
yg

el
Ox

100 0
0 15% 100
Nitrogen 36
 Flammability Diagram - 2
(1) Fuel + (z) Oxygen ---> Products
0 100
Air Line, all combinations of
fuel + air
en

Fu
yg

el
Ox

UFL
Flammable % Fuel in Air
LFL
100
0 100 0
Nitrogen 37
 Flammability Diagram - 3
Air line always extends

FROM: Fuel: 0%, Oxygen: 21% Nitrogen: 79%

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

Equation for this line:

Fuel = -(100/79) Nitrogen + 100

38
 Flammability Diagram - 4
(1) Fuel + (z) Oxygen ---> Products
0 100 CH4 + 2 O2 --> Products
æ z ö
ç ÷ * 100 z=2
è1+ z ø
en

æ z ö
yg

Fu ç ÷ *100 =
Ox

Sto
el è 1+ z ø
ic hi o
me
tric

Flammable
100 0
0 100
Nitrogen 39
 Flammability Diagram - 5
Stoichiometric line always extends from:

FROM: Fuel: 100/(1+z),

Oxygen: 100z/(1+z)
Nitrogen: 0%

TO: Fuel: 0%,

Oxygen: 0%,
Nitrogen: 100%

Equation for this line:

Fuel = (100 – Nitrogen)/(1+z) 40

 Flammability Diagram - 6
(1) Fuel + (z) Oxygen ---> Products
0 100
LOC
en

Fu
yg

el
Ox

UFL

Flammable LFL
100 0
0 100
Nitrogen 41