Professional Documents
Culture Documents
Chapter 2
Chapter 2
1/61
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
2/61
Fires and Explosions
Definitions
Flammability
– Flash Point
– Flammability limits
– Mixtures
– Temperature Dependence
– Pressure Dependence
Minimum Oxygen Concentration
Minimum Ignition Energy
Adiabatic Compression
Ignition Sources
Definitions
Combustion – a chemical reaction in
which a substance combines with an
oxidizer and releases energy.
Explosion – rapid expansion of gases
resulting in a rapid moving pressure or
shock wave.
Mechanical Explosion – due to failure
of vessel with high pressure non
reactive gas.
Explosions
Detonation – explosion (chemical reaction)
with shock wave greater than speed of
sound
Deflagration – explosion (chemical reaction)
with shock wave less than speed of sound
BLEVE – Boiling Liquid Expanding Vapor
Explosion – when liquid is at a temperature
above its atmospheric boiling point. Vessel
ruptures – flammable liquid flashes and
results in a fire/explosion
Explosions
Confined explosion – an explosion
occurring within a vessel or a building.
Usually results in injury to the building
inhabitants and extensive damage.
Unconfined explosion – an explosion
occurring in the open. Usually results
from spill of a flammable gas spill.
These explosions are rarer than
confined since dilution occurs.
Explosions
Dust Explosions - This explosion
results from the rapid combustion of
fine solid particles. Many solid
materials become very flammable
when reduced to a fine powder.
Flammability
Flash Point (FP) – a property of material
used to determine the fire and explosive
hazard. The lowest temperature of a
liquid at which it gives off enough vapor
to form an ignitable mixture with air.
Needs to be determined experimentally.
– Different methods to determine, open cup
and closed cup. Open cup is usually a few
degrees higher.
National Fire Protection Association
Flammability classification
Flammable IA – Flash point < 73°F,
boiling point < 100 °F
Flammable IB – Flash point < 73°F,
boiling point > 100 °F
Flammable IC – 73°F < Flash point <
100 °F
Combustible II – 100 °F < Flash point <
140 °F
Combustible IIIA – 140 °F < Flash point
< 200 °F
Combustible IIIB – Flash point > 200 °F
Flammability Relationships
10/61
Mixture Flash Points
– Flash Points of mixtures can be
estimated only IF one of the components
is flammable. If more than one is
flammable then need to determine
experimentally.
– For mixtures:
Determine the temperature at which the
vapor pressure of the flammable in the liquid
is equal to the pure component vapor
pressure at its flash point.
Mixture Flash Points
Example
– Methanol FP=54°F, Vapor Pressure @ 54°F is 62 mmHg
Determine the flash point of a solution that is 75wt%
MeOH in water.
Solution:
Since only one component is flammable, can estimate
mixture FP:
Mixture Flash Point Example
Continued
Raoult's Law
P xP sat
P 62mmHg
P
sat
98.4mmHg
x 0.63
Now need the temperature that corresponds
to this P sat . Use Antoine's equation (Append II)
ln P A
sat B
C T
T in Kelvin, P sat in mmHg
Mixture Flash Point Example
Continued
Rearrange
B
T sat
C
A - ln P
From Appendix II
A is 18.5875
B is 3626.55
C is -34.29
3626.55
T 34.29 293.36 K
18.5875 ln 98.4
T 20.21C 68.4 F
Flammability Limits
There is usually a
range of compositions
of a flammable vapor
and air where
combustion occurs.
Too little fuel (lean
mixture) not enough
fuel to burn.
Too much fuel (rich
mixture) not enough
oxygen to burn
Flammability Limits
Table 6-1 gives upper flammability
limits and lower flammability limits for
several common substances.
Experimentally determined.
LFL can be estimated from Flash
Point:.
vapor pressure at flash point
LFL
760 mmHg
Determine vapor pressure using Antoine Equation
Mixture Flammability
Limits
Ifyou have a mixture of flammable
components you can calculate Lower
Flammability Limit of the mixture
LFLmix using Le1Chatelier’s
LFLmix n
relationship: yi
LFL
i 1 i
FLAMMABLE
HEL
MIXTURES
LEL
24/61
Flammability LOC
Limiting O2
Concentration:
Vol. % O2 below
Diagram which combustion
can’t occur
1 Atmosphere
25°C
HEL
FLAMMABLE
MIXTURES
LEL
25/61
Flammable Limits Change
With:
Inerts
Temperature
Pressure
26/61
Effect of Temperature on
Lower Limits of Flammability
L
E
L,
%
27/61
Effect of Pressure of
Flammability
Natural Gas, volume%
HEL
LEL
29/61
Minimum Ignition Energy
Effects of Stoichiometry
30/61
Autoignition Temperature
Temperature at which the vapor ignites
spontaneously from the energy of the
environment
Function of:
– Concentration of the vapor
– Material in contact
– Size of the containment
31/61
Flammability Relationships
CONCENTRATION OF FUEL
AUTO
IGNITION
MIST
FLAMMABLE
FLAMMABLE REGION
REGION
TEMPERATURE AIT
FLASH POINT AIT
32/61
Autoignition Temperature
Material Variation Autoignition
Temperature
Pentane in air 1.50% 1018 °F
3.75% 936 °F
7.65% 889 °F
Benzene Iron flask 1252 °F
Quartz flask 1060 °F
Carbon disulfide 200 ml flask 248 °F
1000 ml flask 230 °F
10000 ml flask 205 °F
33/61
Autoignition Temperature
34/61
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
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.
38/61
Classification of Explosions
Rapid Equilibration of High Pressure
EXPLOSION = Gas via Shock Wave
39/61
Potential Energy
10 0.001
100 0.02
1000 1.42
10000 6.53
42/61
Pressure vs Time
Characteristics
DETONATION
OVERPRESSURE
TIME
43/61
CONSEQUENCES
44/61
Bayway, NJ
H-Oil Incident 1970
45/61
46/61
47/61
48/61
Two Special Cases
Vapor Cloud Explosion
Boiling
Liquid /Expanding Vapor
Explosion
49/61
U V C E
N A L X
C P O P
O O U L
N R D O
F S
I I
N O
E N
D S
50/61
What Happens to a Vapor Cloud?
Cloud will spread from too rich, through flammable
range to too lean.
54/61
Vapor Clouds and TNT
World of explosives is dominated by TNT impact
which is understood.
Vapor clouds, by analysis of incidents, seem to
respond like TNT if we can determine the
equivalent TNT.
1 pound of TNT has a LHV of 1890 BTU/lb.
1 pound of hydrocarbon has a LHV of about 19000
BTU/lb.
A vapor cloud with a 10% efficiency will respond
like a similar weight of TNT.
55/61
Multi-Energy Models
Experts plotted efficiency against vapor cloud
size and … reached no effective conclusions.
Efficiencies were between 0.1% and 50%
Recent developments in science suggest too
many unknowns for simple TNT model.
Key variables to overpressure effect are:
– Quantity of combustant in explosion
– Congestion/confinement for escape of combustion
products
– Number of serial explosions
Multi-energy model is consistent with models
and pilot explosions. 56/61
B L E V E
O I X A X
I Q P P P
L U A O L
I I N R O
N D D S
G I I
N O
G N
S
FUEL
SOURCE
58/61
BLEVE Video Clip
59/61
Distance Comparison
INVENTORY UVCE BLEVE FIRE
(tons)
1 120 18 Distance
2 150 36 in Meters
5 200 60
10 250 90 20
20 310 130 30
50 420 200 36
100 530 280 50
200 670 400 60
500 900 600 100
1000 1150 820 130
60/61
DESIGN for PREVENTION
61/61
Eliminate Ignition Sources
Fire or Flames Typical Control
– Furnaces and Boilers – Spacing and Layout
– Flares – Spacing and Layout
– Welding – Work Procedures
– Sparks from Tools – Work Procedures
– Spread from Other Areas jkdj – Sewer Design, Diking,
dkdjfdk dkdfjdkkd jkfdkd fkd Weed Control,
fjkd fjdkkf djkfdkf jkdkf dkf Housekeeping
– Matches and Lighters – Procedures
62/61
Eliminate Ignition Sources
Hot Surfaces Typical Control
– Hot Pipes and Equipment – Spacing
– Automotive Equipment – Procedures
63/61
Inerting – Vacuum Purging
Most common procedure for inerting
reactors
Steps
1. Draw a vacuum
2. Relieve the vacuum with an inert gas
3. Repeat Steps 1 and 2 until the desired oxidant
level is reached
Oxidant Concentration after j cycles:
PL j
y yo( ) where PL is vacuum level
j PH PH is inert pressure
64/61
Inerting – Pressure Purging
Most common procedure for inerting
reactors
Steps
1. Add inert gas under pressure
2. Vent down to atmospheric pressure
3. Repeat Steps 1 and 2 until the desired oxidant
level is reached
Oxidant Concentration after j cycles:
nL j
y yo(n ) where nL is atmospheric moles
j H nH is pressure moles
65/61
Vacuum? Pressure? Which?
Pressure purging is faster because
pressure differentials are greater (+PP)
66/61
Other Methods of Inerting
Sweep-Through Purging
– ‘In one end, and out the other’
– For equipment not rated for pressure, vacuum
– Requires large quantities of inert gas
Siphon Purging
– Fill vessel with a compatible liquid
– Use Sweep-Through on small vapor space
– Add inert purge gas as vessel is drained
– Very efficient for large storage vessels
67/61
Using the
Flammability
Diagram
1 Atmos.
25°C
FLAMMABLE
MIXTURES
68/61
Static Electricity
Sparks resulting from static charge buildup
(involving at least one poor conductor) and sudden
discharge
Household Example: walking across a rug and
grabbing a door knob
Industrial Example: Pumping nonconductive liquid
through a pipe then subsequent grounding of the
container
69/61
Double-Layer Charging
Streaming Current
– The flow of electricity produced by transferring
electrons from one surface to another by a
flowing fluid or solid
– The larger the pipe / the faster the flow, the
larger the current
Relaxation Time
– The time for a charge to dissipate by leakage
– The lower the conductivity / the higher the
dielectric constant, the longer the time
70/61
Controlling
Static Electricity
Reduce rate of charge generation
– Reduce flow rates
BONDING 72/61
Static Electricity – Real Life
73/61
Explosion Proof Equipment
Allelectrical devices are inherent ignition
sources
74/61
Area Classification
Class I Flammable gases/vapors present
National
Electrical Class II Combustible dusts present
Code (NEC) Class III Combustible dusts present but
defines area not likely in suspension
classifications Group A Acetylene
as a function Group B Hydrogen, ethylene
of the nature Group C CO, H2S
and degree of
Group D Butane, ethane
process
hazards Division 1 Flammable concentrations
normally present
present
Division 2 Flammable materials are
normally in closed systems
75/61
VENTILATION
Open-Air Plants
– Average wind velocities are often high enough to
safely dilute volatile chemical leaks
76/61
Summary
Though they can often be reduced in
magnitude or even sometimes
designed out, many of the hazards
that can lead to fires/explosions are
unavoidable
Eliminating at least one side of the
Fire Triangle represents the best
chance for avoiding fires and
explosions
77/61
END of PRESENTATION
78/61