Safety

Determine conditions where fires and /or

explosions can occur.
Develop estimates for upper/lower
flammability limits in mixtures
Utilize inerting to prevent fires/explosions.
Combustion/Fire/Explosion
Energy O H CO O CH + + +
2 2 2 4
2 2
(

= ~
RT
E
A k p kp r
a
O CH CH
exp ,
2 4 4
Where Does Reaction Occur?
In gas phase where ignition source, oxygen
and fuel coexist.
Can be autocatalytic under certain
conditions.
May not need ignition source if temperature
is high enough.
Types of Reactions
Slow Oxidation
Energy can be absorbed by surroundings without
increase in temperature.
Fire
Energy released can be dissipated by environment
with an increase in temperature to a stable point.
Deflagration/Explosion
Energy released cannot be fully dissipated by
environment and temperature continuously
increases.
Definitions
Flash Point Temperature
Enough fuel exists in air to create a flammable
mixture. Will burn out.
Fire Point Temperature
Enough fuel exists in air to create a sustainable
flammable mixture.
Flammability Limits
Volume percent ranges of fuel in air where burning
occurs.
LFL Lower Flammability Limit
Partial pressure of fuel is too low to keep
reaction going
UFL Upper Flammability Limit
Partial pressure of oxygen is too low to keep
reaction going
(

= ~
RT
E
A k p kp r
a
O CH CH
exp ,
2 4 4
Sources for LFL/UFL
MSDS sheets where data was obtained
experimentally.
Mixtures of Fuels
Can be calculated with known LFL/UFL of all
components
Calculating LFL/UFL of Mixtures
1
1
i
i
i
i
i
LFL
y
LFL
UFL
y
UFL
y mole fraction of i on combustable basis
=
=
=

20:80 Hexane/Heptane Liquid at 25

o
C
Assume Liquid is in equilibrium with air in
headspace
Calculate mole fraction of each component
using Raoults Law or suitable model.
Calculate LFL/UFL of mixture
*
* *
ln ,
: 15.8366, 2697.55, 48.78
: 15.8737, 2911.32, 56.51
151.3 , 45.9
0.2 151.3
0.040, 0.048
760
0.040
0.45, 0.5
0.040 0.048
Hexane Heptane
Hexane Heptane
Hex Hep
B
p A Tin K
T C
Hexane A B C
Heptane A B C
p mmHg p mmHg
y y
y y
=
+
= = =
= = =
= =

= = =
= = =
+
5
1
1.20%
0.45 0.55
1.20 1.20
1
7.1%
0.45 0.55
7.5 6.7
0.040 0.048 0.088 8.8%
Mixture
LFL
UFL
y
= =
+
= =
+
= + = =
Temperature Dependence of LFL/UFL
( )
( )
( )
25
25
0.75
25
0.75
25
: , :
T
C
T
C
o
C
LFL LFL T
H
UFL UFL T
H
kcal
where T C H Net Heat of Combustion
gmole
=
A
= +
A
| |
A
|
\ .
T = 20
o
C
1.21, 7.49
1.21, 6.69
1.21, 7.05
0.54 5.40%
Hex Hex
Hep Hex
Mix Mix
Mix
LFL UFL
LFL UFL
LFL UFL
y
= =
= =
= =
= =
Pressure Effects
( )
absolute ls, Megapasca in is P where
P UFL UFL
P
1 log 6 . 20
10
+ + =
Flammability Diagrams
Flammability Diagrams
Compression and Ignition
40% Nitrogen
40% Fuel
20% Oxygen
Original Mixture
40% Nitrogen
40% Fuel
20% Oxygen
Dilute with Air
Original Mixture
40% Nitrogen
40% Fuel
20% Oxygen
Dilute with Air
Air Added
Original Fuel
Constructing Flammability Diagram
1. Draw Air Line
2. Enter LFL & UFL
LFL
UFL
3. Determine z
4. LOC = zLFL
(use data, if available)
Fuel + zO
2
CO
2
+ H
2
O
Constructing Flammability Diagram
LFL
UFL
Fuel + zO
2
CO
2
+ H
2
O
LOC
5. Add Stoichiometric
Line
6. Get Pure Oxygen LFL
and UFL (if available)
. 100
1
z
Stoich
z
=
+
Constructing Flammability Diagram
Fuel + zO
2
CO
2
+ H
2
O
LOC . 100
1
z
Stoich
z
=
+
7. Construct Curve
Flammable
Region
Compression of Gases
1
:
,
,
f
f i
i
f i
f i
p
v
P
T T
P
where
T T are final and initial temperatures, absolute
P P are final and initial pressures, absolute
C
C

| |
=
|
\ .
=
Acrylic Acid Process
Compressor Section
1.4 1
1.4
5
300 475 202
1
458
o
f
o
T K C
Autoignition Temperature for Propylene C

| |
= = =
|
\ .
=
Safety (MSDS) data for hexane


Physical data
Appearance: colourless liquid
Melting point: -95 C
Boiling point: 69 C
Vapour density: 3 (air = 1)
Vapour pressure: 132 mm Hg at 20
C
Specific gravity: 0.659
Flash point: -10 F
Explosion limits: 1.2% - 7.7%
Autoignition temperature: 453 F