Risk Analysis

A methodology to evaluate the probability of an adverse effect of an agent Adverse effect can be loss of limb, loss of life, cancer, or damage due to a fire/explosion The same event can cause various effects, some worse than others Risk is the product of the magnitude of the effect and the probability of it occurring

Chopping Vegetables
Probability of getting a cut is high Consequence is low a nick rather than death The risk is quite low

Chemical Agents
Hazard Identification Determine the dose-response relationship Determine the exposure time Characterize the risk

History
Vitruvious (~100 BC) observed lead toxicity (acidic wine and lead goblets!) John Evelyn linked scrotal cancer with chimney sweepers John Snow linked a London cholera outbreak to a specific contaminated well

Two Approaches

D pot = C (t ) IR (t ) dt
t1

t2

Dose-Response Curves
These are the primary tool for Modelling Effects for chemical exposure (people or animals) No Observable Effect Level (NOEL) threshold below which no effect is observed People are considered 10 times more susceptible than animals

D pot = C (t ) IR(t ) dt
t1

t2

Dose-Response Curves
Dose Response Curves
100 90 80 % of Population 70 60 50 40 30 20 10 0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 Dose (mg/kg) Irritation Systemic Effect Death

Toxic Chemicals Risk

Average body parameters are used
(70 kg mass, 2 L/day water and 20 m3/day air)

Acute Toxicity
LD50 (death within 24 hours) LC50 (death within 24 hours)

Paracelsus (16th century)

The Dose makes the Poison

Toxicity Ranking

Probable Lethal Dose

Units

Chemical Example

LD50 (animals)

Practically >15 non-toxic Slightly toxic 5 - 15 Moderately toxic Very Toxic Extremely toxic Supertoxic 0.5-5 50 500 5 50 <5

g/kg g/kg g/kg mg/kg mg/kg mg/kg Ethanol 10 g/kg

Sodium 4 g/kg chloride Phenobarbital 150mg/kg Picrotoxin Dioxin 5 mg/kg 0.001 mg/kg

Chemical Exposure
Remember some chemicals do not pose acute chemical hazards but have other hazards Polychlorinated biphenyls (PCBs)
LD50 (oral rodents): 1 11 g/kg NOEL (oral - rodents): 12 50 mg/kg for teratogenic, carcinogenic and immunotoxicity

Some chemicals bioaccumulate as well

Epidemiology
The study of factors that affect health and illnesses in populations Disease rates are compared between exposed persons and non-exposed persons Retrospective in nature many diseases have a long latency period Samples sizes need be large Watch for confounding effects (eg., smoking)

Health Effects
For chemical effects, we can model the effects using animal studies or epidemiology Occupational Health and Safety addresses the workplace issues to keep exposures at acceptable levels How to rank various chemicals and/or various process devices for the relative risks?

DOW Chemical Exposure Index DOW Fire and Explosion Index

Methods for identifying and quantifying various release scenarios They provide a dimensionless number that allows for a relative ranking of the risk of the scenario or device

DOW CEI
Used to rank the acute health potential for people in neighbouring communities or plants Suitable for volatile chemicals only Considers liquid or vapour releases from process Scenarios last for 5 minutes

Emergency and Risk Planning Guidelines

ERPG-1: maximum airborne concentration below which all nearly individuals can be exposed for 1 hr without effects (odour threshold or ERPG-2/10) ERPG-2: maximum airborne concentration that nearly all individuals can be exposed for 1 hr without serious health effects (ACGIH TLV) ERPG-3: maximum airborne concentration below which nearly all individuals can work for 1 hr without experiencing life threatening effects (LC50/30 or 5* ERPG-2)

Identify Release Scenarios

Scenarios
Vessel full release in 10 minutes Pipe assume full rupture of 2 pipe
>4 pipe assume loss through 20% of area

PR devices determine total release rate Tank overflows spill = maximum tank input

Airborne Quantity
Gas Release sonic velocity
AQ = 4.751x10 D Pa
2 6

MW T + 273

Pa absolute pressure (kPa); MW mol weight; T temperature (C); D diameter in mm

Liquid Release
Determine liquid release rate and flash fraction
L = 9.44 x10 D l
7 2

1000 Pg

+ 9.8h

Hv Pg - gauge pressure (kPa); l - density (kg/m3) h liquid height above the release point [m]

AQv = 5 Fv L; Fv =

Cp

(Ts Tb )

DOW CEI and Hazard Distance

AQ CEI = 655.1 ERPG 2
AQ HD = 6551 ERPG
Hazard distance is the radius to that concentration

Ammonia Example
Ammonia is stored in a 12 ft diameter by 72 ft long horizontal vessel under its own vapor pressure at ambient temperature (30C or 86F). The largest liquid line out of the vessel is 2 inch diameter (50.8 mm). Pg (pressure inside vessel) = 1064 kPa gauge T (temperature inside vessel) = 30C Tb (normal boiling point) = -33.4C l (liquid density) = 594.5 kg/m3 Cp/Hv = 4.01*10-3 h (height of liquid in tank) = 3.66 m D (diameter of hole) = 50.8 mm MW (molecular weight) = 17.03

Calculations
L = 9.44 x 10 7 (50.8) 2 (594.5) 1000 (1064) + 9.8 (3.66) = 61.9 kg/sec (594.5)

Fv =

Cp Hv

(Ts Tb ) = 0.00401 * [30 (30)] = 0.254

AQ = 61.9 kg/sec; ERPG-2 = 139 mg/m3

AQ CEI = 655.1 = 437 ERPG 2
AQ HD = 6551 = 4,372m ERPG 2

DOW FEI
Simple method for rating the realistic fire or explosion potential of storage or processing equipment Material Factor
intrinsic rate of potential energy release

General Process Hazard Factor

Primary role in magnitude of the loss

Special Process Hazards

Material Factor
NFPA Diamond Health Blue Fire Red Reactivity - Yellow

Liquids or Gases Flammability 1 Non-combustible 2 F.P. > 200 F F.P. > 100F & < 200 F F.P. >73 F & < 100F, OR F.P. < 73 F & B.P. > 100F F.P. < 73 F & B.P. < 100 F Combustible Dust / Mist3 St-1 (Kst < 200 bar m/sec) St-2 (Kst 200 - 300 bar m/sec) St-3 (Kst > 300 bar m/sec) Combustible Solids Dense > 40 mm thick 4 Open < 40 mm thick 5 Foam, fiber, powder, etc. 6 NF = 1 NF = 2 NF = 3 NF = 0 NF = 1 NF = 2 NF = 3 NF = 4

Nr = 0 1 4 10 16 21 16 21 24

Nr = 1 14 14 14 16 21 16 21 24

Nr = 2 24 24 24 24 24 24 24 24

Nr = 3 29 29 29 29 29 29 29 29

Nr = 4 40 40 40 40 40 40 40 40

4 10 16

14 14 16

24 24 24

29 29 29

40 40 40

General Process Factor

A. Exothermic reactions such as alkylation, halogenation or nitration. B. Endothermic reactions such as cracking or pyrolysis. C. Loading or unloading flammables or LPGs or any process such as centrifuging where introduction of air might occur D. For indoor or highly confined units. E. Access from at least two different directions for fire fighting equipment is the aim. F. Good drainage and spill control results in no penalty.

Special Process Factor

Toxicity Sub-Atmospheric Pressure Operation in or near the flammable range Dust Explosion Relief Pressure the pseudo-ratio of operating pressure to the relief pressure. Low Temperature Operation Quantity of Material Corrosion/Erosion Leakage gaskets, seals and packings (also glass devices and bellows) can be sources for leaks Fired Equipment Hot Oil System Rotating Equipment

AREA / COUNTRY

DIVISION

LOCATION

DATE

SITE

MANUFACTURING UNIT

PROCESS UNIT

PREPARED BY:

APPROVED BY: (Superintendent)

BUILDING

REVIEWED BY: (Management)

REVIEWED BY: (Technology Center)

REVIEWED BY: (Safety & Loss Prevention)

MATERIALS IN PROCESS UNIT

STATE OF OPERATION
___ DESIGN ___ START UP ___ NORMAL OPERATION ___ SHUTDOWN

BASIC MATERIAL(S) FOR MATERIAL FACTOR

MATERIAL FACTOR (See Table 1 or Appendices A or B) Note requirements when unit temperature over 140 oF (60 oC)

1. General Process Hazards Base Factor .................................................................................................................

A. B. C. D. E. F. Exothermic Chemical Reactions Endothermic Processes Material Handling and Transfer Enclosed or Indoor Process Units Access Drainage and Spill Control

Penalty Factor Range

1.00 0.30 to 1.25 0.20 to 0.40 0.25 to 1.05 0.25 to 0.90 0.20 to 0.35 0.25 to 0.50

Penalty Factor Used(1)

1.00

__________ gal or cu.m.

General Process Hazards Factor (F1) ................................................................................................. 2. Special Process Hazards Base Factor .................................................................................................................
A. B. C. Toxic Material(s) Sub-Atmospheric Pressure (< 500 mm Hg) Operation In or Near Flammable Range ___ Inerted ___ Not Inerted 1. Tank Farms Storage Flammable Liquids 2. Process Upset or Purge Failure 3. Always in Flammable Range D. Dust Explosion (See Table 3) E. Pressure (See Figure 2) Operating Pressure ________ psig or kPa gauge Relief Setting ________ psig or kPa gauge F. Low Temperature G. Quantity of Flammable/Unstable Material: Quantity _____ lb or kg HC = _____BTU/lb or kcal/kg 1. Liquids or Gases in Process (See Figure 3) 2. Liquids or Gases in Storage (See Figure 4) 3. Combustible Solids in Storage, Dust in Process (See Figure 5) H. Corrosion and Erosion I. Leakage Joints and Packing J. Use of Fired Equipment (See Figure 6) K. Hot Oil Heat Exchange System (See Table 5) L. Rotating Equipment 1.00 0.20 to 0.80 0.50 0.50 0.30 0.80 0.25 to 2.00 1.00

0.20 to 0.30

0.10 to 0.75 0.10 to 1.50 0.15 to 1.15 0.50

Special Process Hazards Factor (F2) ................................................................................................. Process Unit Hazards Factor (F1 x F2) = F3 .................................................................................. Fire and Explosion Index (F3 x MF = F&EI) ....................................................................................
(1) For no penalty use 0.00.

CEI FEI Summary

Easy to use tools Consistent in approach Qualitative in approach they do not look at specific causes and the risk associated with each

Two Approaches

Quantitative Risk Analysis

Generate scenarios for hazardous events Determine the magnitude of the hazard and the probability of its occurring Next identify the mitigation strategy and cost Determine whether mitigation adds value
Remember that adding one safety device may well make another scenario less safe!

Layers of Protection
A process has its normal control systems (operator and computer based) There are emergency safety systems (operator and computer based) There are physical barriers around the plant (curbs and dyking) The plant will have on-site and off-site emergency countermeasures (police, fire department and ambulance).

Scenarios
All scenarios start with an initiating event. If the control system works, the event is dealt with. If the control system does not resolve the issue, then the emergency safety system is activated. If the problem continues, then plant relies on physical barriers. Ultimately, external resources are brought in to address the situation.

Releases
The typical hazard in the CPI is the release of the chemicals A root cause could be the addition of an impurity, when leads to corrosion, which causes a hole when there is a pressure surge. The pressure surge is the initiating event The root cause is the impurity

Liquid Loss Though a Pipe Hole

u = Co 2 Pg

; and Qm = ACo

2 Pg

Co discharge coefficient
approaches 0.61 for sharp edges holes approaches 1 for round holes

Co =

1 1 + Kf

Liquid Loss Though a Tank Hole

u = Co 2 Pg

+ ghL ; and Qm = ACo

2 Pg + 2 ghL

hl is the liquid height above the hole

gPg 1 At o te = ( ) 2( + ghL ) + Co g A 2 Pg

Vapour Losses through a Hole

Qm = ACo Po P ( +1/ ) 2M P 2 / ( ) ( ) RTo + 1 Po Po

Maximum is sonic velocity

Qm ,choked = AC o Po

2 ) ( RTo + 1

( +1) /( 1)

Other Cases
Flashing liquid Liquid Pool evaporation Non-stagnant evaporation Evaporation due to heat from the ground
Qm =

Qm Cp (To Tb ) Mv = H vap
M K A P sat Qm = RTL

MV P Qm = Psys R TL
qg A H vap ; qg =

sat

k s (Tg T )

s t

Dispersion Models
The scenario defines the maximum release rate For vapour releases, the downwind concentrations are determined using a Dispersion Model

Pasquill-Gifford Approach
C ( x, y , z ) = Qm 4 K * x2 + y2 + z2

K* is the eddy diffusivity

Qm 0.5 * y C ( x, y , z ) = exp 2 y z u y
2

z Hr * exp 0.5 * z

z + Hr + exp 0.5 * z

Pasquill-Gifford Stability Class Rural A extremely unstable Rural B moderately unstable Rural C neutrally unstable Rural D neutrally stable Rural E slightly stable Rural F moderately stable Urban A/B moderately unstable Urban C neutrally unstable Urban D neutrally stable Urban E/F moderately stable

y (m) 0.22x * (1 + 0.0001x)-0.5 0.16x * (1 + 0.0001x))-0.5 0.11x * (1 + 0.0001x)-0.5 0.08x * (1 + 0.0001x)-0.5 0.06x * (1 + 0.0001x)-0.5 0.04x * (1 + 0.0001x)-0.5 0.32x * (1 + 0.0004x)-0.5 0.22x * (1 + 0.0004x)-0.5 0.16x * (1 + 0.0004x)-0.5 0.11x * (1 + 0.0004x)-0.5

z (m) 0.20x 0.12x 0.08x * (1 + 0.0002x)-0.5 0.06x * (1 + 0.0015x)-0.5 0.03x * (1 + 0.0003x)-0.5 0.016x * (1 + 0.0003x)-0.5 0.24x * (1 + 0.0001x)-0.5 0.20x 0.14x * (1 + 0.0003x)-0.5 0.08x * (1 + 0.0015x)-0.5

Explosions
Damage due to explosions is caused by the pressure wave Scaled distance z = r/(mTNT)1/3
TNT equivalency is the mass * heat of combustion, divided by 1120 kcal/kg (TNT equivalent) Usually ~3% of energy converted to pressure wave

Effect of Pressure
Effect Occasional breaking of large glass Limited minor structural damage Minor damage to house structures Partial demolition of houses, made uninhabitable Partial collapse of walls and roofs of houses Probable total destruction of buildings Limit of crater lip Overpressure (kPa) 0.2 2.8 4.8 6.9 13.8 69 2000

Scaled Distance
Scaled Distance
100

Pmax (P/Pamb)

10

1 0.1 0.1 1 10 100

0.01 ze (m/kg^1/3)

BLEVE/UVCE
Boiling Liquid Expanding Vapour Explosion Unconfined Vapour Cloud Explosion Release for some time, with ignition found at some distance significant mass of explosive material, and significant damage

Probabilistic Side
Stochastic issues are random events Systemic issues where the design impacts the probability Automobile deaths
Canada - 9 per 100,000 population World 9 per billion km driven

Mostly stochastic, but seat belts have an effect

Statistics
Carcinogenic Risk = D
Product of carcinogenicity in animals, interspecies conversion and dose

Uncertainty

= + +
2 R 2 2

2 D

How Likely is it to go Wrong

Best approach is to use historical data
How frequently does a pump or valve fail?

For events that are follow an initiating event

( S ) = ( IE ) * f ( A IE ) * f ( B IE )...

Testing Frequency
The likelihood of failure on demand increases with the time lag between tests Suppliers (or historical frequency) * ratio of testing frequency to manufacturers frequency

PCF = CF * (TF /TG )

Risk Management
Safety Risk these are usually low probability high exposure/high consequence events; the focus is within the plant boundaries Health Risks these are high probability low exposure/low consequence (or latent consequence) events; the focus here is occupational health Ecological/Environmental Risks these are high probability low exposure/low consequence (or latent consequence) events; the focus is site emissions both local and at great distances Public Welfare/Goodwill Risks this addresses the community or public perception of an organization; a negative impression can lead to a negative impact on sales or negative goodwill from the community Financial Risks this addresses both short term and long term property and financial losses; in essence the business case for risk management

Safety Hazard Identification: Materials involved, quantities, reactivity, initiating events Probability of causes: Likelihood of initiating events and propagating events Consequence Analysis: Nature, magnitude and probability of adverse effects (fires, explosions, and their impact on receptors)

Health Data Analysis: MSDS, and quantities/concentrations of chemicals Exposure Assessment: Pathways and routes for the chemical to enter (exposure rates and time)

Environment Problem formulation: Contaminants, and their effect on flora and fauna Exposure Assessment: Pathways and routes for the chemical to enter (exposure concentrations)

Dose-Response: Toxicity Assessment: Relationship between dose and Relationship between chemical exposure and the impact on the adverse health effect environment Risk Characterization: Integration of toxicity and exposure data (with uncertainty analysis)

Risk Evaluation: Risk Characterization: Integration of probabilities and Integration of toxicity and exposure data (with consequences uncertainty analysis) Fatalities, injuries, economic costs

Individual and population risks Ecosystem and habitat risks

Risk Acceptability
The Zero-Risk Principle - no risk can be tolerated (regardless of its magnitude or the relative benefits)
The world is not a zero risk environment is it better to incur a small risk in order to avoid a larger risk?

The De Minimis Principle - some levels of risk are so trivial that they are not worth worrying about.
often assumed as a lifetime risk of 1 x 10-6.

The De Manifestis Principle - some risks are so obvious that they must be controlled regardless of cost.
a lifetime risk of 1 x 10-3.