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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
Probability of getting a cut is high Consequence is low – a nick rather than death The risk is quite low
Hazard Identification Determine the dose-response relationship Determine the exposure time Characterize the risk
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
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 .
35 Dose (mg/kg) Irritation Systemic Effect Death .15 0.25 0.Dose-Response Curves Dose Response Curves 100 90 80 % of Population 70 60 50 40 30 20 10 0 0 0.1 0.05 0.3 0.2 0.
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 .
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.Toxicity Ranking Probable Lethal Dose Units Chemical Example LD50 (animals) Practically >15 non-toxic Slightly toxic 5 .001 mg/kg .15 Moderately toxic Very Toxic Extremely toxic Supertoxic 0.
carcinogenic and immunotoxicity Some chemicals bioaccumulate as well .rodents): 12 – 50 mg/kg for teratogenic.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 .
smoking) ..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.
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 .
T – temperature (C).751x10 D Pa 2 −6 MW T + 273 Pa – absolute pressure (kPa). D diameter in mm . MW – mol weight.Airborne Quantity Gas Release – sonic velocity AQ = 4.
Fv = Cp (Ts − Tb ) .44 x10 D ρ l −7 2 1000 Pg ρl + 9. ρl .gauge pressure (kPa).Liquid Release Determine liquid release rate and flash fraction L = 9.density (kg/m3) Δh – liquid height above the release point [m] AQv = 5 Fv L.8Δh Hv Pg .
DOW CEI and Hazard Distance AQ CEI = 655.1 ERPG − 2 AQ HD = 6551 ERPG Hazard distance is the radius to that concentration .
03 .01*10-3 Δh (height of liquid in tank) = 3. Pg (pressure inside vessel) = 1064 kPa gauge T (temperature inside vessel) = 30°C Tb (normal boiling point) = -33.8 mm MW (molecular weight) = 17.66 m D (diameter of hole) = 50.Ammonia Example Ammonia is stored in a 12 ft diameter by 72 ft long horizontal vessel under its own vapor pressure at ambient temperature (30°C or 86°F). The largest liquid line out of the vessel is 2 inch diameter (50.5 kg/m3 Cp/Hv = 4.4°C ρl (liquid density) = 594.8 mm).
5) Fv = Cp Hv (Ts − Tb ) = 0.1 = 437 ERPG − 2 AQ HD = 6551 = 4.44 x 10 −7 (50.372m ERPG − 2 .5) 1000 (1064) + 9.Calculations L = 9.00401 * [30 − (−30)] = 0.8) 2 (594.9 kg/sec. ERPG-2 = 139 mg/m3 AQ CEI = 655.254 AQ = 61.8 (3.66) = 61.9 kg/sec (594.
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 .
fiber. etc.300 bar m/sec) St-3 (Kst > 300 bar m/sec) Combustible Solids Dense > 40 mm thick 4 Open < 40 mm thick 5 Foam. OR F.P.P. > 200 F F. < 73 F & B. >73 F & < 100F.P.Liquids or Gases Flammability 1 Non-combustible 2 F.P.P. > 100F & < 200 F F. > 100F F.P. < 73 F & B. powder. < 100 F Combustible Dust / Mist3 St-1 (Kst < 200 bar m/sec) St-2 (Kst 200 . 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 .P.
Exothermic reactions such as alkylation. Good drainage and spill control results in no penalty. F. Endothermic reactions such as cracking or pyrolysis. . Access from at least two different directions for fire fighting equipment is the aim. Loading or unloading flammables or LPG’s or any process such as centrifuging where introduction of air might occur D. halogenation or nitration. E. B. For indoor or highly confined units.General Process Factor A. C.
Low Temperature Operation Quantity of Material Corrosion/Erosion Leakage gaskets.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. seals and packings (also glass devices and bellows) can be sources for leaks Fired Equipment Hot Oil System Rotating Equipment .
................20 to 0.00 0..20 to 0...................... Dust in Process (See Figure 5) H..25 to 2..... E........25 to 1.....75 0.80 0.30 0......... C......... Process Upset or Purge Failure 3........10 to 0..20 to 0......... Rotating Equipment 1...................... Dust Explosion (See Table 3) E.50 0....00 0.......................................... Use of Fired Equipment (See Figure 6) K........... Corrosion and Erosion I.. Toxic Material(s) Sub-Atmospheric Pressure (< 500 mm Hg) Operation In or Near Flammable Range ___ Inerted ___ Not Inerted 1................. F.......... Process Unit Hazards Factor (F1 x F2) = F3 ...25 to 0..... B............................m...25 to 0......................50 0............10 to 1.............................. Liquids or Gases in Process (See Figure 3) 2....20 to 0.................. (1) For no penalty use 0. Quantity of Flammable/Unstable Material: Quantity _____ lb or kg HC = _____BTU/lb or kcal/kg 1............... B..00 1.......30 to 1.......30 0.......15 to 1................. Liquids or Gases in Storage (See Figure 4) 3.. A.15 0.... Pressure (See Figure 2) Operating Pressure ________ psig or kPa gauge Relief Setting ________ psig or kPa gauge F....35 0...... Special Process Hazards Base Factor ..............25 0........00 0...... General Process Hazards Base Factor .......90 0..............80 0. Always in Flammable Range D.............50 Penalty Factor Used(1) 1................ General Process Hazards Factor (F1) .....................50 0......... Low Temperature G....................... Hot Oil Heat Exchange System (See Table 5) L..................00......00 __________ gal or cu..... Leakage – Joints and Packing J... Exothermic Chemical Reactions Endothermic Processes Material Handling and Transfer Enclosed or Indoor Process Units Access Drainage and Spill Control Penalty Factor Range 1... .....50 Special Process Hazards Factor (F2) ...... A.. Tank Farms Storage Flammable Liquids 2................. Fire and Explosion Index (F3 x MF = F&EI) . Combustible Solids in Storage.................40 0...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...... D.......... 2...... C.05 0...
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). .
If the control system works. the event is dealt with.Scenarios All scenarios start with an initiating event. If the control system does not resolve the issue. If the problem continues. then the emergency safety system is activated. Ultimately. . then plant relies on physical barriers. external resources are brought in to address the situation.
which causes a hole when there is a pressure surge. when leads to corrosion. The pressure surge is the initiating event The root cause is the impurity .Releases The typical hazard in the CPI is the release of the chemicals A root cause could be the addition of an impurity.
61 for sharp edges holes approaches 1 for round holes Co = 1 1 + ∑Kf .Liquid Loss Though a Pipe Hole u = Co 2 Pg ρ . and Qm = ACo 2 ρPg Co – discharge coefficient approaches 0.
and Qm = ACo 2 ρPg + ρ 2 ghL hl is the liquid height above the hole gPg 1 At ⎡ o te = ( )⎢ 2( + ghL ) + ρ Co g A ⎢ ⎣ 2 Pg ⎤ ⎥ ρ ⎥ ⎦ .Liquid Loss Though a Tank Hole u = Co 2 Pg ρ + ghL .
choked = AC o Po 2 ) ( RTo γ + 1 γM ( γ +1) /( γ −1) .Vapour Losses through a Hole Qm = ACo Po P (γ +1/ γ ) ⎤ 2M γ ⎡ P 2 / γ ⎢( ) − ( ) ⎥ RTo γ + 1 ⎣ Po Po ⎦ Maximum is sonic velocity Qm .
Other Cases Flashing liquid Liquid Pool evaporation Non-stagnant evaporation Evaporation due to heat from the ground Qm = Qm Cp (To − Tb ) Mv = ΔH vap M K A P sat Qm = RTL MV P Qm = Psys R TL qg A ΔH vap . qg = sat k s (Tg − T ) πα s t .
the downwind concentrations are determined using a Dispersion Model .Dispersion Models The scenario defines the maximum release rate For vapour releases.
y . z ) = Qm 4 π K * x2 + y2 + z2 K* is the eddy diffusivity ⎡ ⎛ Qm ⎢− 0. z ) = exp ⎜σ 2π σy σz u ⎢ ⎝ y ⎣ ⎞ ⎟ ⎟ ⎠ 2 ⎤ ⎧ ⎡ ⎛ z − Hr ⎥ * ⎪exp ⎢− 0.5 * ⎜ ⎨ ⎜ σ ⎥ ⎪ ⎢ z ⎝ ⎦ ⎩ ⎣ ⎞ ⎟ ⎟ ⎠ 2 ⎡ ⎤ ⎛ z + Hr ⎥ + exp ⎢− 0.5 * ⎜ y C ( x. y .Pasquill-Gifford Approach C ( x.5 * ⎜ ⎜ σ ⎢ ⎥ z ⎝ ⎣ ⎦ ⎞ ⎟ ⎟ ⎠ 2 ⎤⎫ ⎪ ⎥⎬ ⎥⎪ ⎦⎭ .
5 0.5 0.5 0.24x * (1 + 0.5 0.08x * (1 + 0.20x 0.16x * (1 + 0.03x * (1 + 0.0001x)-0.32x * (1 + 0.0015x)-0.0001x)-0.0001x)-0.0004x)-0.04x * (1 + 0.0004x)-0.06x * (1 + 0.0003x)-0.20x 0.5 σz (m) 0.5 0.0001x)-0.16x * (1 + 0.5 0.0003x)-0.12x 0.0004x)-0.5 0.5 0.5 0.0001x))-0.0015x)-0.0001x)-0.22x * (1 + 0.14x * (1 + 0.5 .5 0.11x * (1 + 0.016x * (1 + 0.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 σy (m) 0.5 0.08x * (1 + 0.0004x)-0.0001x)-0.11x * (1 + 0.08x * (1 + 0.06x * (1 + 0.22x * (1 + 0.5 0.0003x)-0.5 0.0002x)-0.5 0.5 0.
divided by 1120 kcal/kg (TNT equivalent) Usually ~3% of energy converted to pressure wave .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.
9 13.Effect of Pressure Effect Occasional breaking of large glass Limited minor structural damage Minor damage to house structures Partial demolition of houses.8 6. made uninhabitable Partial collapse of walls and roofs of houses Probable total destruction of buildings Limit of crater lip Overpressure (kPa) 0.8 69 2000 .8 4.2 2.
1 1 10 100 0.01 ze (m/kg^1/3) .Scaled Distance Scaled Distance 100 Pmax (P/Pamb) 10 1 0.1 0.
and significant damage .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.
000 population World – 9 per billion km driven Mostly stochastic.9 per 100.Probabilistic Side Stochastic issues are random events Systemic issues where the design impacts the probability Automobile deaths Canada . but seat belts have an effect .
Statistics Carcinogenic Risk = β κ D Product of carcinogenicity in animals. interspecies conversion and dose Uncertainty σ = σβ + σ + σ 2 R 2 2 Κ 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 φ ( S ) = φ ( 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 = λCF * (TF /TG ) .
Risk Management Safety Risk – these are usually low probability – high exposure/high 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. the focus is within the plant boundaries Health Risks – these are high probability – low exposure/low consequence (or latent consequence) events. in essence – the business case for risk management . 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. the focus here is occupational health Ecological/Environmental Risks – these are high probability – low exposure/low consequence (or latent consequence) events.
magnitude and probability of adverse effects (fires. 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. economic costs Individual and population risks Ecosystem and habitat risks . explosions.Safety Hazard Identification: Materials involved. initiating events Probability of causes: Likelihood of initiating events and propagating events Consequence Analysis: Nature. and their impact on receptors) Health Data Analysis: MSDS. reactivity. quantities. injuries. and quantities/concentrations of chemicals Exposure Assessment: Pathways and routes for the chemical to enter (exposure rates and time) Environment Problem formulation: Contaminants.
some risks are so obvious that they must be controlled regardless of cost. .Risk Acceptability The “Zero-Risk Principle” . often assumed as a lifetime risk of 1 x 10-6. The “De Manifestis 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” . a lifetime risk of 1 x 10-3.some levels of risk are so trivial that they are not worth worrying about.