CM4310: Chapter 5 September 28, 2006

Selection of

Chemical Process Safety Release Incident

Selection of
Figure 4-1 Source Model
Chapter 5: Dispersion Models to Describe
Release Incident
Chapter 4

Wind---> <--Mixing with fresh air--> Selection of

Dispersion Model Chapter 5

Flammable Toxic
Flammable
and/or Toxic?

Chapter 6 Selection of Selection of Chapter 2

Fire and Effect Model
Explosion Model
Source Model for Discharge Mitigation
thru hole Factors

Consequence
Model

Dispersion Models
Dispersion
wind
What? Describe how vapors are transported PLUME PUFF

downwind of a release. Valid between 100 m to

10 km.
• Below 100 m use ventilation equations Chapt. 3. place time & place
Continuous release Instantaneous release
• Above 10 km Æ almost unpredictable.
DOWNWIND DILUTION BY MIXING WITH FRESH AIR
Why? To determine the consequences. ATMOSPHERIC DISPERSION

Results: Downwind concentrations (x,y,z) - Wind speed

- Atmospheric stability: vertical temp. profile
- Roughness ground: buildings, structures, trees, water difficult
Area affected - Height of release above ground level
- Momentum and buoyancy: effective height
Downwind evacuation distances

Atmospheric stability Atmospheric stability

MAINLY DETERMINED BY VERTICAL TEMPERATURE GRADIENT Unstable: Sun heats ground faster than heat can be
+ heat & radiation balance troposphere and surface removed so that air temperature near the ground is higher
- convective air flows Figure 5-3 than the air temperature at higher elevations.
700
LOWER TROPOSPHERE
600
Neutral: The air above the ground warms and the wind
season
• incident sunlight 500 speed increases, reducing the effect of solar input.
time of day
• cloud coverage
Height (meter)

night 400
• wind speed neutral Stable: The sun cannot heat the ground as fast as the
300
ground cools - temperature at ground is lower.
200 day
night STABILITY CLASSES A - F
100

0
A Extremely unstable
-2 0 2 4 6 8 10 12 B Moderately unstable
Temperature (Centigrade) C Slightly unstable Table 5-1
Adiabatic temperature gradient D Neutral
humid air: 0.5 oC / 100 m E Slightly stable
F Moderately stable

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CM4310: Chapter 5 September 28, 2006

Atmospheric stability Release Height Effect

Figure 5-5
High stack

ground level
concentration

Wind-->
Reflected plume
As release height increases,
downwind concentration decreases.
See qualifying notes below table!

Coordinate systems Release Momentum and Buoyancy

Plume MW>29 --> Most hydrocarbons

x
z
Coordinate system

wind Hr y

Jet Release Heavier than air. Gas

Origin at ground level: becomes neutral
Hr = Release Height (x,y,z) = (0,0,0) downwind as it mixes
with air.

Dispersion Models Gaussian form of plume equation Equation 5-49

Dispersion models are based on a mass balance. Qm ⎛ y 2 ⎞ ⎧ ⎡ ( z − Hr ) 2 ⎤ ⎡ ( z + Hr ) 2 ⎤⎫

C ( x, y, z) = exp⎜⎜ − ⎟
2 ⎟ × ⎨exp ⎢− ⎥ + exp ⎢− ⎥⎬
2 πσ y σ z u ⎝ 2σ y ⎠ ⎩ ⎣ 2σ z 2 ⎦ ⎣ 2σ z 2 ⎦ ⎭
Two approaches:
1. Use eddy diffusivities, K, to represent turbulence. Top View of plume
Advantage: nice tidy theoretical model. --> Wind
Disadvantage: K = K(x,y,z), and impossible to measure.
C ( x, y, z ) = Ave. conc. (20-30 min ave)
See text. Qm = Release rate (mass/time)
2. Use dispersion coefficients which represent the standard σ y , σ z = Dispersion coefficients = f(stability class, downwind distance)
u = Wind speed (length/time)
deviations in the concentration profiles.
y, z = Coordinates (length)
Advantage: easy to measure and correlate. H r = Release height (length)

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CM4310: Chapter 5 September 28, 2006

Atmospheric stability Simplified Cases - Plume

Wind Æ
4 4
10 10 Ground Centerline Concentration: X
Fig. 5-10
⎡ 1 ⎛ H ⎞2 ⎤
A A
3 B 3 B
10 10
C
Qm
< C > ( x,0,0) = exp ⎢ − ⎜⎜ r ⎟⎟ ⎥
D
C

(m)
E
(m)

F (5-51)
10
2
10
2
D
πσ yσ z u ⎢⎣ 2 ⎝ σ z ⎠ ⎥⎦
σz
E
σy

1 1
10 10
Ground, centerline, release height Hr = 0
0 0
10 10
1 10 0.1 1 10
0.1
Qm
< C > ( x,0,0) =
Distance Downwind, km Distance Downwind, km (5-48)

Dispersion coefficients for plume model for rural releases. πσ yσ z u

See Figure 5-11 for urban releases, and Table 5-2 for plume
equations. Figure 5-12 and Table 5-3 are for puff model. X is implicit in the dispersion coefficients!

Maximum Concentrations - Plume Puff Equation 5-54

⎡1 ⎛ y ⎞ 2
⎤ ⎧ ⎡ 1 ⎛ z − H ⎞2 ⎤ ⎡ 1 ⎛ z + H ⎞2 ⎤ ⎫⎪
⎥ × ⎪⎨exp⎢− ⎜⎜
Qm*
Always occurs at release point. < C > ( x, y , z , t ) = exp⎢ ⎜ ⎟ r
⎟ ⎥ + exp⎢− ⎜⎜ r
⎟⎟ ⎥ ⎬
2π 3 / 2σ xσ yσ z ⎢ 2 ⎜⎝ σ y ⎟⎠ ⎥ ⎪ ⎢⎣ 2 ⎝ σ z ⎠⎟ ⎥⎦ ⎢⎣ 2 ⎝ σ z ⎠ ⎥⎦ ⎪⎭
⎣ ⎦ ⎩
For releases above ground, max. concentration on ground
occurs downwind.
Hr
2Qm ⎛⎜ σ z ⎞⎟
(σ z ) x ,max H
= r < C >max =
eπuHr ⎜⎝ σ y ⎟⎠
2 t=0 Side view with time
2
1. Use left equation to determine σ z u, t not explicit in equation
2. Use Figures 5-10 or 5-11 to get x. x is implicit thru dispersion coefficients
3. Determine σ y from Figures 5-10 or 5-11. Coordinate system moves with puff center at x=ut
Assume σ x = σ y
4. Calculate <C> from right equation.

Simplified Cases - Puff Location of Puff

y * C
*
*
Constant
Concentration on ground below puff center * C C *

C
* C C concentration

Qm* ⎡ 1 ⎛ H ⎞2 ⎤ x
< C > (0,0,0) = exp ⎢ − ⎜⎜ r ⎟⎟ ⎥
2π 3 / 2σ xσ yσ z ⎢⎣ 2 ⎝ σ z ⎠ ⎥⎦
(5-56)
t0 t1 t2 t3 t4 t5

Same as above, with Hr = 0. Puff center on ground. ---> Wind = constant at u

*
Q (5-41) Center of puff located at: x=ut
< C > (0,0,0) = m

2π 3 / 2σ xσ yσ z

Puff center always at release height.

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CM4310: Chapter 5 September 28, 2006

Maximum Concentration - Puff

Example:
10 kg/s of H2S is released 100 m off of ground.
Always at puff center Estimate the concentration 1 km downwind on
ground? It is a clear, sunny day, 1 PM, wind speed =
3.5 m/s. Assume rural conditions.

X Plume, due to continuous nature of release!

From Table 5-1, Stability Class B.
From Figure 5-10, σ y = 130 m
From Figure 5-10, σ z = 120 m
On ground, max. concentration Use Equation 5-51 for a plume.
always occurs directly below puff
center.

Example: Apply Equation 5-51 Example: Where is max. concentration?

Applies to ground concentration directly downwind of release: Use Equation 5-53: H r 100 m
⎡ 1 ⎛ H ⎞2 ⎤
(σ z ) x ,max = = = 70.7 m
C ( x, 0, 0) =
Qm
× exp ⎢ − ⎜ r ⎟ ⎥ 2 1.414
πσ yσ z u ⎢⎣ 2 ⎝ σ z ⎠ ⎥⎦
Use equation in Table 5-3 to determine downwind distance:

10.0 kg/s ⎡ 1 ⎛ 100 m ⎞2 ⎤ σ Z = 0.12 x

C ( x, 0, 0) = × exp ⎢ − ⎜ ⎟ ⎥
(3.14)(130 m)(120 m)(3.5 m/s) ⎢⎣ 2 ⎝ 120 m ⎠ ⎥⎦ 70.7 m = 0.12 x
C ( x, 0, 0) = 41.2 × 10 kg/m = 41.2 mg/m
-6 3 3 x = 590 m
At this location, from Figure 5-10:
Use Equation 2-7 to get 29.7 ppm. TLV-TWA is 10 ppm.
σ y = 92 m

Use Equation 5-52 to calculate max. concentration: Example: What is max. discharge to result in 10 ppm?

( )
Hr
2 Qm ⎛ σz ⎞ (2)(100 kg/s) 70.7 m
Maximum will occur at same location: ( σ z ) x ,max =
2 ⎜ ⎟=
< C > max = 2
eπ uH r ⎝ σ y ⎠
2
(2.718)(3.14)(3.5 m/s)(100 m) 92 m 10 ppm = 13.9 mg/m3 (Equation 2-7)
Substitute into Equation 5-52:

< C > max = 5.14 × 10

−4
kg/m = 514 mg/m = 370 ppm
3 3 2Qm ⎛ σz ⎞
< C >max = ⎜σ ⎟
⎝ y⎠
2
eπ uH r

-6
13.9 × 10 kg/m =
3 2Qm

(2.71)(3.14)(3.5 m/s)(100 m)
2 ( 70.71 m

92 m
)
Qm = 2.7 kg/s Not very much!

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CM4310: Chapter 5 September 28, 2006

Example:
Example:
10 kg of H2S is released instantly on the ground. What is
concentration at fenceline 100 m away? Same conditions as How long does it take for puff to reach fenceline?
before.
From Table 5-1, stability class is B.
x = ut
At x = 0.1 km, from Figure 5-12: σ y = 10 m σ z = 16 m
x 100 m
Use Equation 5-41 for a ground release, centerline conc.: t= = = 28.6 s after release.
* u 3.5 m/s
Qm
< C > (0, 0, 0) =
2π σ xσ y σ z
3/ 2

Very little time for an emergency response!

Assume σ x = σ y
* 6
Qm = 10 kg = 10 × 10 mg
3
<C> = 79.4 mg/m = 571 ppm

Example: Isopleths
What size release will result in 10 ppm at fenceline?
What: Lines of constant concentration
Same procedure as for plume. Answer is 0.175 kg = 175
gm.
Plume:

Not very much! Better to contain chemicals than to

mitigate after a release! 10 ppm boundary
Puff:

Determining Isopleths: Plume and Puff Procedure to Determine Isopleths - 1

Divide equation for centerline concentration by 1. Determine concentrations along centerline at

equation for ground level concentration. Solve for y, fixed points downwind.
which is crosswind direction.
Wind

⎛ < C > ( x,0,0, t ) ⎞

y = σ y 2 ln⎜⎜ ⎟⎟ (5-45)
⎝ < C > ( x, y ,0, t ) ⎠ Release point

2. Use equation (5-45) to find y at each fixed

Downwind, ground Isopleth conc. point.
centerline conc.

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CM4310: Chapter 5 September 28, 2006

Procedure to Determine Isopleths - 2 Procedure to Determine Isopleths - 3

3. Plot +y and - y at each fixed point. 4. Connect the points.

Wind Wind

Release point Release point

Isopleth

Worst Case on Ground- Plume and Puff Dense Gas Dispersion

Want maximum <C> downwind

Qm
Plume: Centerline, ground, Hr = 0 < C > ( x,0,0) =
πσ yσ z u Britter-McQuaid Dense Gas
Dispersion Model:
Puff: Center of puff on ground, Hr = 0
Qm* Based on dimensionless groups and
< C > ( x,0,0) = available experimental data.
2π 3 / 2σ xσ yσ z u
See pages 195-199.
Specify: Qm and Qm* at maximum Heavier than air!
σ ' s are minimum --> F stability
u is minimum within stability class --> 2 m/s
(EPA suggests 1.5 m/s!)

Dense Gas Dispersion Toxic Effect Criteria

What concentration should we use for emergency releases?
Transition from
dense to neutrally Cannot use PEL or TWA since these are for continuous
buoyant work exposures – values are too low for short-term
exposures.
ERPGs – Emergency Response Planning Guidelines, issued
by American Industrial Hygiene Association
EEGLs – Emergency Response Guidance Levels, issued by
Results in shorter distances if only dense gas. National Academy of Sciences/National Research Council.
Results in longer distances if dense gas coupled with
Gaussian dispersion. LOC – Level of Concern from EPA
Toxic Endpoints promulgated by EPA as part of RMP

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CM4310: Chapter 5 September 28, 2006

ERPG: Emergency Response Planning ERPG: Emergency Response Planning

Guideline Guideline

ERPG-1: max. airborne concentration below which it is ERPG-3: max. airborne concentration below which it is
believed nearly all individuals can be exposed for up to 1-hr believed nearly all individuals can be exposed for up to 1-
without experiencing effects other than mild transient hour without experiencing or developing life-threatening
adverse health effects or perceiving a clearly defined health effects.
objectionable odor.
Table 5-6 ERPG-1 ERPG-2 ERPG-3
ERPG-2: max. airborne conc. below which it is believed
Ammonia 25 ppm 200 ppm 1000 ppm
nearly all individuals can be exposed up to 1 hr without
experiencing or developing irreversible or other serious Chlorine 1 ppm 3 ppm 20 ppm
health effects or symptoms that could impair their ability to
Monomethylamine 10 ppm 100 ppm 500 ppm
take protective action.
Toluene 50 ppm 300 ppm 1000 ppm

EEGL: Emergency Exposure Guidance Levels IDLH: Immediately Dangerous to Life and
Health
A concentration of a gas, vapor, or aerosol that is judged
acceptable and allows exposed individuals to perform A concentration that poses a threat of exposure to airborne
specific tasks during emergency conditions lasting from 1 to contaminants when that exposure is likely to cause death or
24 hours. immediate or delayed permanent adverse health effects or
Table 5-7 prevent escape from such an environment.
1-hr EEGL 24-hr EEGL
Available from OSHA (osha.gov) or NIOSH Pocket Guide.
Ammonia 100 ppm
Chlorine 3 ppm 0.5 ppm
Ammonia 50 ppm
Toluene 200 ppm 100 ppm
Chlorine 10 ppm
Toluene 500 ppm

LOC: Level of Concern Toxic Endpoints

The max. concentration of an extremely hazardous Must be used for dispersion modeling required for the EPA
substance in air that will not cause serious irreversible RMP. Values are, in order of preference, ERPG-2 or LOC.
health effects in the general population when exposed to the
substance for relatively short duration.
See EPA for values.
Ammonia 0.14 mg/L Table 5-8
Chlorine 0.0087 mg/L
Chloroform 0.49 mg/L

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CM4310: Chapter 5 September 28, 2006

Proposed Hierarchy to Estimate Values

Proposed Hierarchy to Estimate Values (con’t)
Table 5-9: ORDER IS REVERSED IN TABLE!
Primary Secondary Benzene
Primary Secondary Benzene
ERPG-1: PEL-STEL 50 ppm
ERPG-3: EEGL (30-min) 1000 ppm TLV-STEL 5 ppm
3 x TLV-TWA 30 ppm
IDLH 500 ppm
ERPG-2: EEGL (60 min) 150 ppm
LOC
PEL-C
TLV-C
5 x TLV-TWA 50 ppm