SECTION I: INTRODUCTION Process safety emphasizes the use of appropriate technological tools to provide information for making safety decisions with respect to plant design and operation. Safety, hazard, and risk are frequently-used terms in chemical process safety. Their definitions follow: • Safety or loss prevention is the prevention of accidents by the use of appropriate technologies to identify the hazards of a chemical plant and to eliminate them before an accident occurs. • A hazard is anything with the potential for producing an accident. • Risk = [Frequency of a hazard resulting in an accident] x [Consequence of the accident]. Chemical plants contain a large variety of hazards. First, there are the usual mechanical hazards that cause worker injuries from tripping, falling, or moving equipment. Second, there are chemical hazards. These include fire and explosion hazards, reactivity hazards and toxic hazards. Nature of the Accident Process Chemical plant accidents follow typical patterns. It is important to study these patterns in order to anticipate the types of accidents that will occur. As shown in Table 1, fires are the most common, followed by explosion and toxic release. With respect to fatalities, the order reverses, with toxic release having the greatest potential for fatalities. Table 1: Three Types of Chemical Plant Accidents Type of accident Probability of Potential for Potential for occurrence fatalities economic loss Fire High Low Intermediate Explosion Intermediate Intermediate High Toxic Release Low High Low Economic loss is consistently high for accidents involving explosions. The most damaging type of explosion is an unconfined vapour cloud explosion where a large cloud of volatile and flammable vapor is released and dispersed throughout the plant site followed by ignition and explosion of the cloud. Toxic release typically results in little damage to capital equipment but personnel injuries, employee losses, legal compensation, and cleanup liabilities can be significant. The Accident Process Accidents follow a three-step process. Initiation: the event that starts the accident. Propagation: the event or events that maintain or expand the accident. • Termination: the event or events that stop the accident or diminish it in size. In the example cited above, the worker tripped to initiate the accident. The shearing of the valve and the resulting explosion and fire propagated the accident. The event was terminated by consumption of all flammable materials.
• •


Process upsets Process deviations Pressure, Temperature Flow rate, Concentration, Phase /state change, Impurities Reaction rate/ heat of reaction Spontaneous reaction Polymerization, Runaway reaction Internal explosion Decomposition Containment failures Pipes, tanks, vessels, gaskets/seals Equipment malfunctions Pumps, valves, instruments, sensors, interlock failures Loss of utilities Electricity, nitrogen, water, refrigerator, air, heat transfer fluids, steam, ventilation • • • • • •

Table 2 Accident Initiating Events Management Human errors systems failures Inadequate Design staffing Construction Insufficient training Operations Lack of administrative controls and audits Maintenance Testing and inspection

External events Extreme weather conditions Earthquakes Nearby accidents’ impacts Vandalism / sabotage

Table 3 Accident Propagating Factors Failures: Equipment failure, Safety system failure Ignition sources: Furnaces, Flares, Incinerators, Vehicles, Electrical switches, Static electricity, Hot surfaces, Cigarettes Management systems failure: Inadequate staffing, training etc Human errors: Omission, Commission, Fault diagnosis, Decision making Domino effects: Other containment failures, Other material releases External conditions: Meteorology, Visibility • • • • Table 4 Accident Phenomena Discharge: Single (liquid/vapour) or two phase flow, flash, evaporation Dispersion: Neutral or buoyant gas, Dense gas Fires: Pool fires, Jet fires, Flash fires, Fireballs Explosions: BLEVEs, Confined explosions, Unconfined vapor cloud explosions, Physical explosions, Dust explosions, Detonations, Missiles

Table 5 Accident Consequences • Effect analysis: Toxic effects, Thermal effects, Overpressure effects • Damage assessments: Community, Workforce, Environment, Company assets, Production Risk Analysis and Management Risk analysis, as used for the assessment of the hazards associated with process plant and storage installations can be summarized by three questions. - What can go wrong? - What are the effects and consequences? - How often will it happen? The first and basic step of hazard identification (the first question) is purely qualitative and is often called a safety study. Such a study may reveal aspects of the plant or installation which require more consideration. It is then necessary to answer the next two questions in order to complete the risk analysis. The results of the analysis are used for judgment about the acceptability of the risk and for decision making (see figure below). Qualitative answers are often given to the second and third questions. However, recent developments have involved the application of quantitative techniques for obtaining answers to these two questions. The use of these techniques is termed as quantitative risk analysis (QRA). The whole exercise may be called risk assessment. In earlier years, many companies did not use quantitative techniques after the identification stage. However, decisions were made and actions taken to control specific hazards considering (qualitatively) probabilities and consequences. In a sense this is an elementary form of risk analysis, but at a less sophisticated level than assessments involving quantitative consideration of probabilities and consequences. However, over the years, the use of in-depth risk assessment ranging from hazard identification to computation of individual and societal risk has increased. Risk Control and Layers of Protection Safety engineering involves eliminating the initiating step and replacing the propagation steps by termination events Table 6 presents a few ways to accomplish this. In theory, eliminating the initiating step can stop accidents. In practice this is not very effective. It is unrealistic to expect elimination of all initiation. A much more effective approach is to work on all three areas to insure that accidents, once initiated, do not propagate and will terminate as quickly as possible. Risk Measures Risk is defined as a measure of economic loss or human injury in terms of both the likelihood and the magnitude of the loss or injury. There are three commonly used ways of combining information on likelihood and magnitude of loss or injury: risk indices are single numbers or tabulations that yield simple presentations, individual risk measures consider the risk of an individual who may be at any point in the effect zones of incidents, and societal risk measures consider the risk to populations that are in the effect zones of incidents.


System Description Hazard Identification Scenario Identification

Accident Probability

Accident Consequence Modify Design No Accept Risk?

Risk Estimation

Yes Build System/Operate

Schema of Risk Assessment and Management Table 6: Mitigating the Accident Process Procedure Grounding and Bonding Inerting Flame proof electricals Guardrails and guards Maintenance procedures Hot-work permits Human factors design Process design Awareness of dangerous properties of chemicals Emergency material transfer Reduce inventories of flammables Equipment spacing and layout Nonflammable construction materials Firefighting equipment and procedures Relief systems Sprinkler systems Installation of check and emergency shut-off valves

Step Initiation

Desired effect Diminish






Operator Supervision Typical Layers of Protection • Individual Risk: risk to a person in the vicinity of a hazard (probability of fatality person per year) • Societal Risk: a measure of risk to a group of people. The number of incidents evaluated in a QRA may be very large. comparison of risk reduction benefits from various remedial measures) or an absolute basis (e.g. Risk presentation reduces this large volume of information to a manageable form. The end result may be a 5 . residential. This definition can include the population (e. societal risk estimation requires a definition of the population at risk around the facility.g. This individual risk is independent of the number of people present – it is the same for each of the 400 people in the building during office hours and for the single guard at other times.Layers of Protection (Fig. the likelihood of people being present. The presentation may be on a relative basis (e. Risk presentation provides a simple quantitative risk description useful for decision making. the likelihood of 10 fatalities at a specific location (x.g. The difference between individual and societal risk may be illustrated by the following example. 2) Community Emergency Response Plant Emergency Response Physical Protection (Dikes) Physical Protection (Relief Devices) Automatic Action SIS or ESD Critical Alarms. Manual Intervention Basic Controls. Additionally. Process Alarms. than at other times when a single person is affected. comparison with a risk target). each individual in that building is subject to a certain individual risk. y) is a type of societal risk measure. An office building located near a chemical plant contains 400 people during office hours and 1 guard at other times. The calculation of societal risk requires the same frequency and consequence information as individual risk. or mitigation factors. Risk Presentation The large quantity of frequency and consequence information generated by a Quantitative Risk Analysis (QRA) must be integrated into a presentation that is relatively easy to understand and use. If the likelihood of an incident causing a fatality at the office building is constant throughout the day. industrial. However. Operator Supervision. school). For example. The form of presentation will vary depending on the goal of the CPQRA and the measure of risk selected. the societal risk is significantly higher during office hours. when 400 people are affected.

individual risk contour plot). 101-1000). 11-100. population concentrations) may be quickly identified.g. A logarithmic plot is usually used because the frequency and number of fatalities range over several orders of magnitude. Acceptable Risk One cannot eliminate risk entirely. For a single chemical process in a plant comprised of several process. it is necessary to make every effort to minimize risks within the economic constraints of the process as well as ensure compliance with the national regulatory (acceptable) risk standards. 6 . Individual risk representation Common form of presentation of Individual Risk is risk contour plots (Figure 3). a graph (e. The presentation of societal risk was originally developed for the nuclear industry. Figure 4 shows an F-N curve for a single liquefied flammable gas facility. hospitals. 1-10. Risk contours (“isorisk” lines) connect points of equal risk around the facility. Every chemical process has a certain amount of risk associated with it. 5 below. A common form of societal risk is known as an F-N (Frequency-Number) curve. Risks from a process plant environment are always greater than the normal day-to-day risks taken by individuals in their non-industrial environment.g. The approach to risk management followed today is based on the ALARP (as low as reasonably practicable) principle. and/or a risk map (e. Societal risk representation Societal risk addresses the number of people who might be affected by hazardous incidents. Certainly it would require a substantial effort and considerable expense to design a process with a risk comparable to the risk of sitting at home.g. schools. F-N plot). this risk may be too high since the risks due to multiple exposures are additive.g. It is also common to show contributions of selected incidents to the total F-N curve as this is helpful for identification of major risk contributors. which is a three tiered framework as illustrated in Fig. An F-N curve is a plot of cumulative frequency versus consequences (expressed as number of fatalities). Another form of societal risk presentation is a tabulation of the risk of different group sizes of people affected (e. From an engineering perspective. At some point in the design stage someone needs to decide if the risks are "acceptable". a table. Places of particular vulnerability (e.single-number index.

3 14.5 x 10-5 Construction 5 10 x 10-5 Sector 7 .Individual Risk Contours around a Plant Fig 3 Individual Risk (Iso-risk) Contours around a Process Facility Societal Risk Profile (F – N Curve) around a Plant Accident Frequency Actual Averaged Number of Fatalities in the Community Fig. 4 Societal Risk Profile (F – N Curve) around a Plant Table 7 Risks to life from employment FAR Risk per person per year Firemen in London 1940 1000 2000 x 10-5 Policemen in Northern Ireland 1973-1992 70 140 x 10-5 Offshore oil and gas 62 125 x 10-5 Health and Safety Executive tolerable limit 50 100 x 10-5 Deep sea fishing 42 84 x 10-5 Coal mining 7.

4 x 10-5 2.05 9.4 x 10-5 2.2 1.e.1 x 10-5 FAR= number of fatalities in 108 working hours. i. Table 8 Risks to life from employment (Guidelines) Risk per person per year Maximum tolerable risk: 10-3 • employees 10-4 • public 10-5 • public (nuclear) Broadly acceptable risk: 10-6 • employees and public Negligible risk: 10-7 • employees and public Fig.2 x 10-5 0.05 0..2 0.1 x 10-5 0.3 x 10-5 1. in a group of 1000 people for a working lifetime.7 1.6 0.8 4 3. 5 Framework for Risk Criteria: As Low as Reasonably Practicable (ALARP) Intolerable risk (Risk cannot be justified The ALARP region Risk is undertaken only if a benefit is desired Tolerable only if risk reduction is impracticable or if its cost is grossly disproportionate to the improvement gained Broadly acceptable region (no need for detailed QRA to demonstrate ALARP) 8 .Railways All premises covered by the Factories Act (UK) Agriculture Chemical and allied industries All manufacturing industry Vehicle manufacture Clothing manufacture UK Health and Safety Executive broadly acceptable limit 4.6 x 10-5 8 x 10-5 7.

GV = Cd APS {(γ M / RT ) X }0. such that: X =( 2 (γ +1) /(γ −1) ) γ +1 . Cd = discharge coefficient (~ 0. Examples of Emission Source (Emergency Unplanned Releases) Gas discharge • Hole in equipment (pipe.9 bar absolute will result in sonic flow. Thus for releases of most industrial gases to atmosphere.. In the above formula where ps = absolute upstream (storage pressure (N/m2).71 to 2. vessel) containing gas under pressure • Relief valve discharge (of vapor only) • Generation of toxic combustion products as a result of fire Two-phase discharges • Hole in pressurized storage tank or pipe containing a liquid above its normal boiling point • Relief valve discharge (e. R = gas constant (8314 J/kg-mol /oK). T = storage pressure (N/m2) and temperature (oK). PS. A = hole area (m2). dimensionless) Typical values of γ range from 1.(2) ⎛ Ps ⎞ ⎛ γ +1 ⎞ If ⎜ ⎟ > ⎜ ⎟ ⎝ Pa ⎠crit ⎝ 2 ⎠ γ /( γ −1) Then the velocity if gas discharging from the leak is sonic.5 9 . γ = gas specific heat ratio (Cp/Cv. We define X.g.SECTION II: ACCIDENT EFFECT ANALYSIS Table below shows the various accident scenarios and consequences feasible in an industrial scenario. 1..(3) Gas mass flow rate through an orifice is given by: . due to runaway reaction or foaming liquid) Liquid discharges • Hole in atmospheric storage tank or other atmospheric pressure vessel or pipe under liquid head • Hole in vessel or pipe containing pressurized liquid below its normal boiling point The following sections show the methodology of estimating their effects quantitatively.67.. pa = absolute downstream (atmospheric pressure (N/m2). M = gas molecular weight (kg/kg-mol). GAS DISCHARGE γ /( γ −1) ⎛ γ +1 ⎞ We define a ratio r = ⎜ ⎟ ⎝ 2 ⎠ .05.(4) Where GV = gas discharge rate (kg/s)..1 to 1.(1) . which give ‘r’ values of 1.. upstream pressures over ~ 1.8).

3 barg At P = 10 barg.81 m/s2). Therefore use a gas discharge equation.8){π (0.. g = acceleration of gravity (9. X =( Thus X= 0. ρl = liquid density (kg/m3).8)(2) 490 = 1.15 × 44 /(8314 × 298)}(0. Therefore use the liquid discharge model.15.0.e. the discharge must be as a pure gas.09kg / s 2.e.64. A= discharge hole area (m2). LIQUID DISCHARGES Discharge of pure (i. sharp edged orifices is 0.ρl-1)](TsCpl)-1/2 where GLV is total two-phase emission mass rate (kg/s) Λ is latent heat of vaporization (J/kg) is gas density at storage pressure (kg/m3) ρg Ts is the storage temperature (oK) Cpl is specific heat of liquid (K/kg/oK) 10 . the flow is sonic. p = liquid storage pressure (N/m2 absolute).e.74. pipe length > 0. Thus. Data: Propane heat capacity ratio = 1.5 kg/s 3.35 2 (γ +1) /(γ −1) ) γ +1 GV = (0. Cd = discharge coefficient (dimensionless).. which exceeds r = 1..5 = 0. Here Ps /Pa = 5.01) 2 / 4}(5 ×105 )[{1. Example: Calculate the discharge of propane from a tank through a 10-mm hole at 10 barg. the discharge will initially be liquid. Data: Propane density = 490 kg/m3.0/1. p = 10 barg = 11 x 105 N/m2 abs pa = 1 x 105 N/m2 abs GL = CdAρl 1/ 2 2( p − pa ) ρl + 2 gH = (0.6 – 0.01) 2 4 (490) 2(10)(10 5 ) + 2(9. Propane vapor pressure 25oC = 8.61) π (0. pa = downstream (ambient) pressure (N/m2 absolute)..35)]0.Example: Calculate the discharge rate of propane through a 10-mm hole for conditions of 25oC and 4 barg (5 bara).1 m). Propane vapor pressure 25oC = 8.. TWO-PHASE FLOW If the liquid is stored at saturation (i.3 barg Since the total pressure is less than the vapor pressure of propane. p = pvp) and equilibrium two-phase choked flow is established during release through a severed pipeline (i. then the following equation is recommended: .0 = 5.(5) + 2 gH ⎟ ρl ⎝ ⎠ Where GL = liquid mass emission rate (kg/s). 25oC with 2 m liquid head. H = height of liquid above hole (m) The discharge coefficient for fully turbulent discharges from small.(6) GLV = [AΛ/(ρg-1. nonflashing) liquids through a sharp-edged orifice/nozzle is given by: ⎛ 2( p − pa ) ⎞ GL = CdAρl ⎜ .

43 ⎝ 340000 ⎠ Flashing liquids escaping through holes and pipes require very special consideration since two-phase flow conditions may be present.Tb) oK . The equations describing incompressible fluid flow through holes apply. nonequilibrium conditions exist. If the fluid path length through the release is greater than 10 cm (through a pipe or thick-walled container)..e boiling point at 5 bar = 130oC) Tb = atmospheric boiling point (69oC) Hvap = latent heat of vaporization at Tb = 3.65 200 0. If the fluid path length of the release is very short (through a hole in a thin-walled container).85 50 0.(7) x < p(ρg-1. in Eq.P sat ) . that accounts for frictional losses. a fraction. f. stored at temperature above the normal boiling point). If this condition is not met. F. The result will only be valid for liquids stored at a pressure higher than the saturation vapor pressure. equilibrium flashing conditions are achieved and the flow is choked.. then a more complicated numerical model is necessary to calculate the emission rate. respectively.(9) 11 . A good approximation is to assume a choked pressure equal to the saturation vapor pressure of the flashing liquid. the fluid flashes external to the hole. GLV. Several special cases need consideration. and the liquid does not have time to flash within the hole.e.55 400 4. Suggested values for F are given in Table 2. This fraction is approximated from the thermodynamic relationship ΔT = (T .(6) should be multiplied by a factor.This equation applies only if the following condition is met: . Hvap the heat of vapourization at normal pressure. where Lp and D are pipe length and diameter. Data Cp = average liquid heat capacity (range T to Tb) ~2400 J/kg/oK T = operating temperature (i.4 x 105 J/kg Hence FV = 2400 ⎜ ⎛ 130 − 69 ⎞ ⎟ = 0.ρl-1)(TsCpl)/Λ2 Where x is the weight fraction of vapor after depressurizing to atmospheric pressure. Frictional losses for saturated liquids For long pipe lengths the mass emission rate. of the liquid emission is "flashed" to vapor as the pressure is reduced to ambient. Table 2: Variation of Factor F with Ratio Lp/D Lp/D F 1 0 0.. FRACTION FLASHED FROM LIQUID DISCHARGE For superheated liquids (i.75 100 0.. Example: Leak of hexane from a pressurized pipeline at 5 bar. With this assumption the mass flow rate is given by Gm = ACo 2ρ f gc (P .(8) FV = CpΔT/Hvap Where Ts is process line/vessel temperature and Tb is normal boiling point temperature.

(10) v fg C pT Small droplets of liquid also form in a jet of flashing vapor. A leak of diameter 0.774 kg/s 12 . At these conditions. for propylene.0945 m) 2 / 4 x 2(603 kg/m 3 ) [1(kg m/s 2 ) / N] (1.968 x 106 Pa and its density is 603 kg/m3.P sat ) = (0. Cp = 2.61.4 x 106 Pa.85 x 10 -5 m 2 = (3. and Psat is the saturation vapor pressure of the flashing liquid at ambient temperature.0945 m forms in the tank. Estimate the mass flow rate through the hole. Solution. two-phase mass flow rate is given by: ΔH v A g c GLV = . ΔHv = 3. For liquids stored at their saturation vapor pressure. The saturation vapor pressure of liquid ammonia at this temperature is 0. psat = 1.18 x 10 1.34 x 105 J/kg) (1 N m/J) Cp T 0. Equation 10 is used.4 x10 6 − 0. A is the area of the release. ρf is the density of the liquid (mass/volume).042 m 3 / kg x ( ( ) ) (2.61) (3.85 x 10-5 m2 ΔH v A v fg gc 7. Co is the discharge coefficient (unitless).968 x 10 6 ) (N / m 2 ) Gm = 97.. P = Psat. Assume a discharge coefficient of 0. Determine the mass flow rate through the leak.Example Liquid ammonia is stored in a tank at 24oC and a pressure of 1. These aerosol droplets are readily entrained by the wind and transported away from the release site. The area of the leak is πd 2 (3. P is the pressure within the tank.15 x 106 Pa.18 x 103 J/kg K Equation 10 applies to this case. Gm = ACo 2ρ f gc (P . GLV = ( ) 2 = 7. A 1-cm diameter hole develops in the tank. vfg = 0. Equation 9 applies for the case of equilibrium flashing conditions.0(kg m/s 2 ) / N 3 J/kg K ( 298 K) (1N m/J) ) GLV = 0. For this case the choked.14 ) 1 x 10 . The assumption that the quantity of droplets formed is equal to the amount of material flashed is frequently made. Example: Propylene is stored at 25oC in a tank at its saturation pressure.042 m3/kg.6 kg/s Where.14)(0. Equilibrium flashing conditions can be assumed.2 m = A= 4 4 Using Equation 54.34 x 105 J/kg.

neutral conditions.(12) 2 Where Dm is the molecular diffusivity of the vapor I air (m /s) d is the effective pool diameter (m) Nsh is the Sherwood number. and it is necessary to model the evaporation from a surface pool.(13) 2 Where km is the kinematic viscosity of the air (m /s) u is the wind speed at 10 m over the pool (m/s) DISPERSION MODELS Gases can be released either continuously (plume) or instantaneously (puff). E. moderately conditions. C. moderately unstable conditions. Extremely unstable conditions. F. D.8-15200] . Plumes refer to with the travel time (time for cloud to reach location of 13 .. b Neutral and Positively Buoyant Plume and Puff Models Neutral and positively buoyant plume or puff models are used to predict concentration and time profiles of flammable or toxic materials downwind or a source based on the concept of Gaussian dispersion.5. then an empirical formula for slowly evaporating pools can be applied.b Surface wind Daytime insolation Nighttime conditions speed (m/s) at 10m height Strong Moderate Slight Thin overcast ≤ 3/8 or ≥ low 4/8 cloudiness cloudiness B A-B A <2 F E C B A-B 2-3 E D C B-C B 3-4 D D D C-D C 4-6 D D D D C >6 A. and the liquid is well mixed. Once released.e. they will be dispersed by atmospheric conditions.037(km/Dm)1/3[(ud/km)0..(11) Where Ge is the evaporative emission rate (kg/s) A is the pool area (m2) pvp is the vapor pressure (N/m2) M is the molecular weight (kg/kg-mol) * R is the gas constant (J/mol/oK) Tp is the pool temperature (oK) The parameter kg is the mass transfer coefficient (m/s). the pool temperature is within a few degrees of ambient and the liquid does not boil). B. slightly conditions. TABLE 3 Pasquill Stability Meteorological Conditionsa.. SLOWLY EVAPORATING POOL In many cases the hazardous material does not evaporate before it hits the ground surface. If the rate of evaporation is light to moderate (i. The dispersion phenomenon depends on whether the gas is lighter or heavier than air. slightly unstable conditions. For light to neutrally buoyant gases the following table allows the choice of applicable stability class (table 3) which in turn is used to choose the dispersion coefficients provided in tables 4 and 5.. given by the formula Kg = DmNsh/d . Ge = kgApvpM/R*Tp . given by the correlation NSh = 0.

73 0. it is often assumed σx = σy.087x1. u = wind velocity (m/s) Dispersion coefficients σy and σz for diffusion of Gaussian plumes are available aa predictive formulas for these are also available.135x0. H = height of source above ground level plus plume rise (m). σz = dispersion coefficients (m). function of distance downwind.14x0. z . Use of such formulas allow for easier computerization of the method.92 D 0.082x0.067x0. y = crosswind.91 D 0.15x0.057x0.04x0.92 A 0.10x0. σy.90 C 0. Table 4 Equations for Pasquill – Gifford Dispersion Coefficients for Plume Dispersion (x = distance downwind from source) Pasquill-Gifford Stability class σz(m) σy (m) or σx (m) 0. The basis for the PasquillGifford model is Gaussian dispersion in both the horizontal and vertical axes.10x 0.y. Also because of a lack of data.92 C 0. y. M = amount released instantaneously (kg).53x0.70 E 0.88 B 0.89 F 0.18x0.71 0.65 0. σz).493x A 0.60x0. FORMULA FOR INSTANTANEOUS PUFF EMISSIONS: ⎡ M y2 −( x − ut ) 2 −( z − H ) 2 −( z + H ) 2 ⎤ C ( x.91 E 0.92 0.80 Table 5 Equations for Pasquill – Gifford Dispersion Coefficients for Puff Dispersion (x = distance downwind from source) Pasquill-Gifford Stability class σz(m) σy (m) or σx (m) 0. these differ slightly.88 0. y .093x0. z = vertical) c = concentration (kg/m3) at location x.10 0.06x 0.90 0.z = distance from source.112x0.92 0.(15) Where. t ) = exp{ ]}⎥ − 2 }{[ exp + exp ⎢ 2 (2π )3/ 2 σ xσ yσ z ⎢ 2σ x 2σ y 2σ z2 2σ z2 ⎥ ⎣ ⎦ . t = time elapsed after release (s) Puff emissions have different spreading characteristics from continuous plumes and different dispersion coefficients (σy.(14) Where x.interest) or sampling (or averaging) time (normally 10 min).34x0..337x 0.09x 0.63 14 .195x 0.128x0.82 F 0. GV = vapour emission rate (kg/s).05x0.95 0.02x 0.90 0. z.85 0. m (x = downwind. FORMULA FOR CONTINUOUS PLUME DISPERSION: ⎡ GV − y2 ⎤ ⎡ −( z − H ) 2 −( z + H ) 2 ⎤ exp{ 2 }⎥ ⎢exp{ } + exp{ }⎥ C= ⎢ 2πσ yσ z u ⎢ 2σ y ⎥ ⎣ 2σ z2 2σ z2 ⎦ ⎣ ⎦ .75 B 0.

. Weather conditions correspond to D stability. Gas constant.128x0. Cppm =C ⎡ − y2 ⎤ ⎡ −( z − H ) 2 −( z + H ) 2 ⎤ exp 2 ⎥ ⎢exp + exp ⎢ ⎥ 2πσ yσ z u ⎢ 2σ y ⎥ ⎣ 2σ z2 2σ z2 ⎦ ⎣ ⎦ ⎡ −102 ⎤ ⎡ −(2 − 1) 2 −(2 + 1) 2 ⎤ 0. 10 m crosswind.85 = 5. Explosions can arise from strictly physical phenomena such as the catastrophic rupture of a pressurized gas container or from a chemical reaction such as the combustion of a flammable gas in air.25 = 3. EXPLOSIONS AND FIRES The objective of this section is to review the types of models available for estimation of accidental explosion and fire incident outcomes. Then. When explosions arise from a combustion reaction usually the thermal radiation effects are ignored because the shock wave effects will predominate.3 = + exp exp exp ⎢ ⎥⎢ ⎥ 2π (9. Ambient temperature.3) ⎣ 2(9. within buildings or vessels) or an unconfined state (i. These latter reactions can occur both in a confined state (i. This equilibrium must be rapid enough that the energy contained in the high-pressure gas is dissipated as a shock wave. Chlorine molecular weight.082)(293) x 106 = (2. the plume is constrained by ground level. The consequences of concern for explosions in general are shock wave overpressure effects and projectile effects. Data: Assume ground roughness is equivalent to urban conditions..e. The following accident scenarios are considered: • Unconfined Vapor Cloud Explosions and Flash Fires • BLEVE and Fireball • Pool Fire and Jet Fires 15 . R = 0.72 x 10-4 kg/m3 To convert this into ppm (vol). unconfined vapor cloud explosions or UVCE).4) 2 ⎦ G RTa (0. Ta = 20oC (293oK). 5 m/s wind (at 10 m height). σz = 0.e. so the mean height for wind estimation is selected as 2 m. for fires the consequences of concern are thermal radiation effects.3 m/s Dispersion coefficients for D stability evaluated at x = 120 m (using table above) σy = 0. thus dispersion will rapidly ensure that the dense gas behaviour zone is negligible and a Gaussian model is adequate. The leak rate is small.Example on Plume Discharge: Calculate the concentration of chlorine from a source of 0.4)(3.5) 2 ⎦ ⎣ 2(5. The release occurs at 2 m. and 2 m height.093x0. assume that the plume is at near ambient temperature (Ta). pressure p = 1 atm abs. Mo = 71.90 = 9.72 x 10-4) x 106 = 92 ppm PM o (1)(71) 2. An explosion can be thought of as a rapid equilibrium of a high-pressure gas with the environment.3 kg/s located 2 m above ground level at a place 120 m downwind.5)(5.5 m.4 m Concentration in kg/m3 can be found from Equation (14): C= = 2. Stability class = D.082 m3 atm/kg-mol/oK The following equation is used to estimate the wind speed at a height of 2 m can be determined: uz = u10 (z/10)p = 5(2/10)0.4) 2 2(5.

• Peak overpressures of UVCEs are much less than with detonations. M = mass of flammable material released. a vapor cloud forms and disperses. Two important mechanisms for flame acceleration are thermal expansion and turbulence. and positive phase durations of 20-100 ms. thus if many pieces of process equipment and many structures are present. η = empirical explosion yield (or efficiency) (ranges from 0. Process structures contribute to partial confinement and turbulence. factored by an explosion yield term: ηME c W= . it is likely that a flash fire will make the transition a UVCE.Unconfined Vapor Cloud Explosions and Flash Fires When a large amount of a volatile flammable material is rapidly dispersed to the atmosphere.. It is based on the assumption of equivalence between the flammable material and TNT. a UVCE or flash fire will occur. Ec = lower heat of combustion of flammable gas (kJ/kg or Btu/lb). If this cloud is ignited before the cloud is diluted below its LFL. • Materials with higher fundamental burning velocities can produce easier transition to UVCE for a given release quantity. The main consequence in a UVCE is the shock wave that results while the main consequence in a flash fire is the thermal radiation. typically 1 bar (15 psi) or less. A model of UVCEs is the TNT model. Scaled overpressure as a function of scaled distance 16 .(16) E cTNT where W = equivalent mass of TNT (kg or lb). Various researchers have concluded that • There may be some minimum mass of flammable material that is required to allow transition from a flash fire to UVCE.10). • The presence of some confinement/obstacles may be necessary for transition to UVCE.01 to 0. The TNT model is easy to use and has been applied for many CPQRAs. These estimates range from 1 ton to 15 tons. Figure 1. EcTNT = heat of combustion of TNT (44374765 kJ/kg or 1943-2049 Btu/lb.

This section describes the methods used to calculate the effects of the vessel rupture and the fireball that results if the released liquid is flammable and is ignited.48 M0.325 .(20) Initial ground level hemisphere diameter (m) Dinitial = 1. Assume an explosion yield (η) = 0. E = surface emitted flux (kW/m2) F21= view factor (dimensionless) The atmospheric transmissivity τ. x = path length. Assume EcTNT = 4650 kJ/kg From Equation (16). If the released liquid is flammable.02(Pwx)-0. calculate the distance to 5 psi overpressure (equivalent to heavy building damage) of an UVCE of 10 short tons of propane. The initial diameter is used to describe the short duration initial ground level hemispherical flaming-volume before buoyancy forces lift it to a semisteady height. Converting scaled distance to real distance: RG = ZG W1/3 = 7 m/kg1/3 x (4530 kg)1/3 = 113 m 0. however..(21) where M = initial mass of flammable liquid (kg).Example Using the TNT equivalent model. distance from flame surface to target (m) 17 . weakening the container and leading to sudden shell rupture. This causes a reduction in radiation received at target locations. Data: Mass = 10 tons..26 . A pressure relief valve does not protect against this mode of the failure. the scaled distance (ZG) to 5 psi (Pso m/kg1/3. It should be noted.33 atm) = 7 BLEVE and Fireball A Boiling Liquid Expanding Vapor Explosion (BLEVE) occurs when there is a sudden loss of containment of a pressure vessel containing a superheated liquid or liquefied gas..05..000 x 46350 4650 = = 4530 kg From Figure above.825 M0. The radiation received by a target (for the duration of the BLEVE incident) is given by QR = τEF21 . a fireball may result. Lower heat of combustion of propane (Ec) = 46350 kJ/kg.(23) where τ = atmospheric transmissivity (fraction energy transmitted: 0 to 1). Pw = water partial pressure (Pascals.(19) Center height of fireball (m) HBLEVE = 0. Useful formulas for BLEVE physical parameters are Peak fireball diameter (m) Dmax = 6.. This is sufficient to generate a pressure wave and fragments. W = ηME c E cTNT = 0. is an important factor.09 .3 Dmax . typically increasing its volume over 200 times. that a BLEVE can occur due to any mechanism that results in the sudden failure of containment allowing a superheated liquid to flash. The correlation formula that accounts for humidity is: τ = 2..75 Dmax . A BLEVE is a sudden release of a large mass of pressurized superheated liquid to the atmosphere The primary cause is usually an external flame impinging on the shell of a vessel above the liquid level. Thermal radiation is absorbed and scattered by the atmosphere. N/m2).(22) where QR = radiation received by a black body target (kW/m2) τ = transmissivity (dimensionless).05 x 10.(18) Fireball duration (s) tBLEVE = 0.

Frad MH c . Pool fire models have been applied to LNG spills as well as more common flammable materials. dikes.(25) F21 = 2 4r where F21 = view factor between sphere and target surface.. D2 ..4. pool size is fixed by the size of release and by local physical barriers (e. the maximum diameter is reached when the product of burning rate and surface area equals the 18 . typically 0.Thermal radiation is usually calculated using surface emitted flux. Hc = heat of combustion (kJ/kg). They tend to be localized in effect and are mainly of concern in establishing the potential for domino effects and employee safety zones. Pool Size: In most cases.12 (LPG). The most common application of jet fire models is the specification of exclusion zones around flares. as the latter requires the flame temperature. rather than for community risk. Pool and jet fire models. For a continuous leak. Frad = radiation fraction. rather than the Stefan-Boltzmann equation.g.. D = sphere diameter (m) r = distance from sphere center to target along the ground (m) BLEVE Schematic Dmax HBLEVE X Target r Pool Fires and Jet Fires Pool fires and jet fires are common fire types resulting from fires over pools of liquid or from pressurized releases of gas and/or liquid. The surface heat flux is based on the radiative fraction of the total heat of combustion. TBLEVE= fireball duration (s) As the effects of a BLEVE mainly relate to human injury. on an infinite flat plane. Pool Fire Models Burning Rate: Large pool fires burn at a constant vertical rate. Typical heat fluxes in BLEVEs (200-350 kW/m2) are much higher than in pool fires as the flame is not smoky. Dmax = peak fireball diameter (m). are made up of a range of independent submodels and the best pool fire model will be based on the selection of the most appropriate submodels. M = mass of LPG in BLEVE (kg).40. unlike those for dispersion and UVCE.25-0.(24) E= π ( Dmax ) 2 t BLEVE where E = surface emitted flux (kW/m2).05 kg/m2s (gasoline) to 0. a geometric view factor for a sphere to a surface normal to the sphere (not the horizontal or vertical components) should be used. This fraction is typically 0.25-0. characteristic for the material. sloped drainage areas). Typical values for hydrocarbons are in the range 0. E.

Ec = heat of combustion.0 x 106 = 5. m2 Q = 0..Example: Determine the thermal flux received at a distance of 100 m from a pool fire contained in a 25-m-diameter tank dike.09 = 2. The simplest shape factor is the point source that assumes all radiation arises in a single point and is received by an object oriented perpendicular to this: .66 x 0. This must be applied to the total heat output. Typical values of H/D are in the range 2-3. A = pool area./5 x 25)2 m2 = 2.(26) Fp = 1/ 4π x 2 -2 Where Fp = point source view factor (m ). kg/m2s.09 = 0. vapor pressure of water at 50% relative humidity and 20oC = 232 Pa Procedure: (1) Ignore flame tilt as there is no wind (2) Estimate total heat released Q = MbEcA where Mb = burning rate. Data: burning rate = 013 kg/m2s. Received Thermal Flux: The received thermal flux (on a target) from a pool fire is given by Qx = τQRFp .700 kJ/kg.8 x 105 kW. The surface emitted power unit per area can be estimated using the radiation fraction method as follows: (i) Calculate total combustion power (based on burning rate and pool area) (ii) Multiply by radiation fraction to determine total power radiated (iii) Determine flame surface area (commonly use only the cylinder side area) (iv) Divide radiated power by flame surface area. more rigorous formulas or tables are used. τ = atmospheric transmissivity (dimensionless).. QR can be estimated.02(2320x100)-0. where dikes lead to square or rectangular shapes.13 kg/m2s x 43. x = distance from point source to target (m).35 x 2. 20oC and 50% relative humidity. heat of combustion = 43. At closer distances. as this radiant fraction is high for smoky pool fires) then the radiant heat. but smoke obscuration often reduces this to 20-60 kW/m2. Geometric View Factor: The thermal radiation received at a target location is determined by the geometric view factor (ignoring atmospheric absorption). QR = total heat radiated (kW).02(Pwx)-0. an equivalent diameter may be used. The point source view factor provides a reasonable estimate of received flux at distance far from the flame.66 The received thermal flux at 100 m is then calculated using Equation (27) Qx = τQRFp = 0. Fp = point source view factor (m-2) 19 .35 (conservative. kJ/kg. Upper values for other hydrocarbon pool fires lie in the range 110-170 kW/m2.8 x 106 kJ/s = 2. QR = 0.15-0. The radiation fraction of total combustion power is often quoted in the range 0.35. View factors are discussed in texts on thermal radiation.98 x 106 Kw x 8. Weather conditions are no wind.2 kW/m2 leakage rate. Surface Emitted Power: LPG and LNG fires radiate up to 250 kW/m2.700 kJ/kg x π (0.8 x 106 kW = 9.8 x 106 kW Assume radiant fraction for hydrocarbon fires = 0. not to the flux per unit area.0 x 106 m-2 2 2 4πx 4π 100 Using Equation (23) for a distance of 100 m: τ = 2. Circular pools are normally assumed. Flame Height: Many observations of pool fires show that there is an approximate ratio of flame height to diameter.(27) 2 Where Qx = thermal radiation received at distance x (kW/m ). FP = 1 1 = = 8.

72 4.36 3.29 4..25 3.48 4.19 4.50 = 1.56 4.82 3.72 3. This relationship is tabulated in Table 6.12 4.67 4. The probit variable Y is related to the probability P (of a specified level of response) by: Y −5 ⎛ u2 ⎞ 1 . overpressure due to an explosion or radiation intensity due to a fire).9x1000.33 4.5 = 45 m W = 0. W = jet flame conical half-width at flame tip (m). but several reviews have been published. Here dose refers to the intensity of accident outcome (air-borne concentration of a toxic material.80 4.96 4.59 3.39 4.23 4.36 4.95 .05 4.85 4.69 4.50 = side-on hazard range to 50% lethality (m.75 4.12 3.53 4.42 4.45 3. the side-on hazard zone for 50% lenthality is 54 m from the jet flame centerline.(29) .(30) Rs..(28) L = 9.92 4.5 = 91 x 250. The probit relationship of Equation 31 transforms the typical sigmoid shape of the normal response versus does curve into a straight line when plotted using a linear probit scale.47 where L = length of torch flame (m).87 4.(31) P= exp ⎜ − ⎟du ∫ ⎝ 2⎠ 2π −∞ Equation A provides a relationship between the probability P and the probit variable Y.4 m0. M = LPG release rate (kg/sec. while response implies the human/property damage caused by the accident. the probit (probit = probability unit) method is particularly suited. From Equations (28)-(30) the jet flame dimensions are determined: L = 9.95 3. t = exposure time (s.92 3. Table 7 shows a variety of probit equations for a number of different types of exposures.9 t0.82 4. are given by (for LPG): .9 t0. rs..52 3.97 20 Table 6: The Transformation from Percentages to Probits 0 1 2 3 4 5 6 7 8 -2. The dimensions of the torch flame which is assumed to be conical. For single exposures.5 W = 0.08 4.87 3.90 4. but subject to 1< m< 3000 kg/s)..50 4.25L .4 m0. The probit variable Y is computed from the following equation: Probit = Y = k1 + k2 ln V % 0 10 20 30 40 .4 x 250.50 = 1.01 4..1 m0.66 4. but subject to 10<t<300s)The end-on hazard zone is 85% of the side-on hazard zone.64 4.61 4.67 2.25L = 11 m (half width) rs.16 4. The causative factor represents the dose.77 4.59 4.1 m0.26 4. V. Example: Determine the 50% lethality range for a pressurized release of LPG @ 25 kg/s lasting for 100s.( 32) 9 3.47 = 54 m Thus.Jet Fire Models: Jet fire modeling is not as well developed as for pool fires. Standard curve fitting techniques are used to determine the best fit straight line. ESTIMATION OF EFFECTS OF ACCIDENTS: PROBIT ANALYSIS Many methods exist for representing the response-dose curve.45 4.47 = 1. but subject to r>W).77 3.

56 teIe4/3/104 te= effective time of exposure (s). For a probit of 3. For a probit of 4.74 6. the probability is 100%.2 7.13 5. For a probit less than 2.51 5.09 Examples: 1.88 0.33 5.50 5.05 (or 5%) 5.00 5.41 5. Table 7: Probit correlations for exposures. the probit is 5.75 5.6 1. 21 .50 60 70 80 90 % 99 5.58 5.46 5.36 the probability is 0.81 6.61 5.93 o p Structural damage -23.05 5.99 6.10 5. the probability of fatality is 50%.41 0.65 5.47 5.58 5.13 6.8 7.1 2. the probability is 0.84 3. Type of injury or damage Causative Probit variable Parameters V k1 k2 Fire: Burn deaths from fire -14.92 po Glass breakage -18.09.55 0.992 (or 99.01 .04 6.08 5.5 7.29 + 0.34 0.995 (or 99.28 0.95 the probability is 0.08 6.8 (or 80%).33 5. For a probability of 0.64 0.75 0.91 po Eardrum ruptures -15.95 6.55 5.29 0.58 4.88 6.72 2.52 5.92 ln (602 x 60) = 5.3 7.64 5.48 (or 48%) 6.1 (or 10%) .44 5.71 6.8 2.28 5.2%) 7.36 5.0 7.29 + 0.05 0.5%). 8.36 the probability is 0.1 7.6 7.15 5.67.18 5.31 5. For a probit more than 8.20 5.03 5.88 5.4 7. the causative variable V is representative of the magnitude of the exposure. For a probit of 7. For a probability of 0.77 6.84 6.92 ln (C2t) = – 8.25 5.7 7.9 2.92 C2T C= concentration (ppm).48 0.33 0.92 6.1 6.9 8. For a probability of 0.23 7. Ie= effective radiation intensity received by target (W/m2) Explosion: Deaths from lung hemorrhage po -77.67 6.41 5.Using table 3.37 5.23 5. Ychlorine = – 8. the probit is 7. the probit is 3.18 7.39 5. T= time interval (min) Example: What is the chance of human fatality for a 60 min exposure to 60 ppm chlorine? Ans: From table 5.79 o 2 p = peak overpressure (N/m ) Toxic release: Chlorine deaths -8.

91 ln p0 Now p0 = 5 psi = (5/14. complete demolition of houses Relatively high blast overpressures (>15 psig) are necessary to produce fatality (primarily due to lung hemorrhage). The probit method has found less use for thermal injury than it has for toxic effects. Thus. 5. A probit model to estimate injury levels for a given thermal dose from pool and flash fires.56 ln tI 4/ 3 /10000 Where Pr = probit.5 psi) 90% glass breakage No fatality and very low probability of injury 70 mbar (1 psi) • Internal partitions & joinery damaged. 22 .(33) nuclear explosion data. 15psi overpressure is the approximate threshold for fatality. Limiting flux for secondary fires.68 The probability of fatality is ~ 1%. also. I = thermal radiation intensity (W/m2) Table 8 Explosion Impact Criteria Explosion Overpressure Effect • • 35 m bar (0. No fatality 140 mbar (2 psi) • House uninhabitable and badly cracked 210 mbar (3 psi) • Reinforced structures distort • Storage tanks fail • 20% chance of fatality to a person in a building 350 mbar (5 psi) • House uninhabitable • Wagons and plant items overturned • Threshold of eardrum damage • 50% chance of fatality for a person in a building and 15% chance of fatality for a person in the open 700 mbar (10 psi) • Threshold of lung damage • 100% chance of fatality for a person in a building or in the open. the chance is negligible) If overpressure is 15 psi (1 atm): Y = – 77. Incapacitation. leading to fatality unless rescue is effected quickly.9 + 2. Example: What is chance of death from lung hemorrhage for an exposure to 5 psi blast pressure? From Table 7 Yfatality from hemorrhage = – 77.Table 9 Thermal Radiation Impact Criteria Criterion Level (kW/m2) 40 20 12.1 + 6.1 Threshold value below which escape should always be possible. based on .5 Likely Effects at Criterion Level Immediate fatality.7) x 101300 N/m2 = 34455 N/m2 Hence Y = – 77.91 ln (103365) = 2.91 ln 34455 = – 4.. Extreme pain within 20 seconds and movement to shelter is instinctive. t = duration of exposure (sec).9 (From table 6.1 + 6.1 + 6. but can be repaired • Probability of injury is 10%. is: Yburn deaths = – 14.

especially for short duration incidents such as BLEVEs (on the order of 10-20s). the component fails after a certain period of time. 0 The time interval between two failures of the same component is called the mean time to failures (MTTF) and is given by the first moment of the failure density function: E(t) = MTTF = ∫ f(t)dt = λ 0 ∞ 1 . i. 23 . 000) 4 / 3 /10000 ⎤ = 3. Equation (33) can be rearranged to solve for the thermal radiation intensity I: For t = 10 s. With adequate data it can be shown that. For 50% fatality.(4) Equations 1through 5 are only valid for a constant failure rate.9 + 2. Determine the thermal flux necessary to cause 50% fatalities for 10 and 100 seconds of exposure. t) is given by: . Pr = 5.. The probability the component will not fail during the time interval (0. Equation 1 assumes a constant failure rate. the failure rate is reasonably constant and Equation 2 through 4 are valid. and is given by .(3) The area under the plot of complete failure density function is unity.(2) P(t) = 1 .(1) R(t) = e-λt where. I = ⎡104 e[(Pr + 14. when t the reliability goes to 0. The overall probability of a failure in a process is dependent on the nature of this interaction. I = 11 kW/m2 This example demonstrates the importance of duration of exposure. Data is collected on the failure rate of a particular hardware component.9) / 2.. Many components exhibit a typical "bathtub" failure rates.00 ⎣ ⎦ Hence using table 6 the chance of fatality is ~ 2 % 2.e. ∫ f(t)dt = 1 . SECTION III: RELIABILITY THEORY Equipment failures or faults in a process occur as a result of a complex interaction and failures of the individual components. Yburn deaths = –14. Between these two periods. A fixed criterion. This is called the average failure rate and is represented by λ with units of faults/time. P. R is the reliability.. may be inappropriate for such incidents. suitable for prolonged exposures. What is the chance of human fatality for 20s exposure to 20kW/m2? Using Eq 33 (or table 7).0 (Table 4). For t = 100 s.e-λt The failure density function f(t) is defined as: f(t) = dP(t) = λ e−λ t dt ∞ .R(t) = 1 . The failure rate is highest when the component is new (due to defects in manufacturing/assembly) and when it is old (due to wear and tear in aging). Using the probit method. I = 61 kW/m .56] / t ⎤ ⎣ ⎦ 2 3/ 4 . . on the average.56 ln ⎡ 20(20.9 + 2.Example 1. λ..56 ln tI 4 / 3 /10000 = – 14. The complement of the reliability is called the failure probability (or sometimes the unreliability).

is: Rsys = ∏R i =1 n i =1 n i .044 Strip chart recorder 0. in that.60 Hand valve 0. Process components also interact in series.52 Thermometer 0. or top event.(7) .(8) Psys = 1. In such cases the overall process failure probability is computed from the individual component failure probabilities..(5) where n is the total number of components and Pi is the failure probability of each. Rsys = 1 - ∏ (1 .044 Level measurement meter (liquids) 1.. In some cases. These values depend on manufacturing practices employed by manufacturer. Events in fault 24 .70 Pressure gauge 1. design of the component. The approach starts with a well-defined accident. These are average values determined at a typical chemical process facility. a process failure requires the simultaneous failure of a number of components operating in a "parallel" mode. Table 1 Failure Rate Data for various selected process components Instrument Faults/year Controller 0.44 FAULT TREES Fault trees are a deductive method for identifying ways in which hazards can lead to accidents.Interaction between Process Units Accidents in chemical plants are usually the result of a complicated interaction between a number of process components.29 Control valve 0.022 Pressure switch 0. materials of construction.22 Thermocouple 0. In such a case the system unreliability is: Psys = ∏P i =1 n i .. Rsys.Pi ) Failure rate data for a number of typical process components are provided in Table 1.R ) i i =1 n .027 Valve positioner 0.. the physico-chemical environment in which the component functions etc.14 Solenoid valve 0.∏ (1 . For series components the overall system process reliability. and works backwards towards the various scenarios or events that can cause the accident.(6) Where Ri is the reliability of an individual process component.42 Stepper motor 0.41 Pressure relief valve 0.13 Alarm Indicator lamp 0. they are connected in a "Series" structure within a system. Process components interact in two different ways.

Below is an example of a fault tree for a reactor system for which 2 safety systems are available (i) an alarm system and (ii) a shutdown system. It can also include software failure. For reasonably complex chemical processes. The AND logic gate is used for describing processes that interact in parallel. and environmental abnormities. Exothermic Reactor System 25 . OR gate is used for describing events that need occur alone to result in output event. a number of additional logic functions are needed to construct a fault tree. human error.tree are not restricted to hardware failures.

Four safety functions are identified. This system features a high temperature alarm that has been installed to warn the operator of a high temperature within the reactor. The final safety feature is invoked by the operator performing an emergency shutdown of the reactor. The event tree for a loss of coolant initiating event is shown in the next figure.Fault Tree for Exothermic Reactor System EVENT TREES An event tree begins with an initiating event and works towards a final result or consequence through steps. The second safety function is the operator noticing the high reactor temperature during normal inspection. The third safety function is the operator re-establishing the coolant flow by correcting the problem within time. 26 . The event tee approach includes the effects of an event initiation followed by the impact of the safety systems on the propagation of the accident based on the performance of the safety systems. The first safety function is the high temperature alarm. When an accident occurs in a plant. various safety systems come into operation in order to prevent the accident from propagating. These safety systems may in turn either fail or succeed in their operation. Example: Consider the chemical reactor system shown in Figure below. In constructing the event tree these safety functions are written across the page in the order in which they logically occur. The operator may also notice the high temperature on his own during normal inspection.

Exothermic Reactor System If in a certain situation a safety function does not apply or is not relevant. the horizontal line is continued through the safety function without branching. The sequence description and consequences are indicated on the extreme right hand side of the event tree. The open circles indicate safe conditions and the circles with the crosses represent unsafe conditions. 27 .

Event Tree for the Exothermic Reactor System 28 .

the following realistic scenarios are identified for X: I. For example. when the information is needed. • Incident consequences are simple step functions. The probability of fatality from a hazardous incident at a particular location is either 0 or 1. as well as HAZID techniques. fault and event tree models Define QRA objectives and describe system Identify hazards and incident scenarios Estimate incident consequences Estimate incident frequency Estimate risk Use results to manage and reduce risk QRA Procedure Incident Identification It is important to choose the correct set of representative accident scenarios for QRA. and is used primarily to illustrate the QRA methodology. flammable liquid from a pipe might catch fire immediately (jet fire). where most phenomena occur as simple step functions. The atmospheric stability class and wind speed are always the same. • Only two weather conditions occur. Half of the time the wind blows from the northeast. In the company X the following apply: • All hazards originate at a single point. Using industry-wide historical data. depending on the sequence of events which follows the original incident. Estimation of accident consequence: source and dispersion models 2. The specific population distribution will be described later in the example. and the description of the impact zones of incidents as simple geometric areas. Incident Outcomes The identified incidents may have one or more outcomes. Estimation of Accident frequency: reliability. • There are people located around the site. These simple conditions. Estimation of effects of accident effects on human and property: probit Analysis 3. a leak of volatile.QRA: A CASE STUDY The chemical plant X considered is a very simple one. An explosion resulting from detonation of an unstable chemical. These models include: 1. might form a flammable cloud which 29 . toxic gas resulting from failure of a vessel. A release of a flammable. allow easy hand calculation of various risk measures. II. The concepts and techniques used to derive the risk measures from the underlying incident frequency and consequence information are the same as would be used for a more complex QRA study (steps shown in Fig below ) which use a variety of models. and half of the time it blows from the southwest.

differentiated by the weather conditions and wind direction. the release of flammable. this is represented by an event tree with no branches (Fig 2). or property – for example. resulting in a toxic vapor cloud. the environment. Incident Event Tree for Incident I I – Explosion Incident Outcomes Incident Outcome Cases II – Explosion Event Tree for Incident II IIA – Ignition IIA – Ignition (Explosion) IIB1 – Toxic Cloud to Southwest IIB – No Ignition Toxic Cloud IIB2 – Toxic Cloud to Northeast II – Flammable Toxic Gas Release Fig 2.could ignite and burn (flash fire) or explode (vapor cloud explosion). toxic gas. toxic material dose-response relationships (probit equations). if these conditions influence the potential damage resulting from the incident.0). Event tree logic may be used to identify the incident outcomes and outcome cases. vapor cloud fire. Consequence and Impact Analysis Incident impact estimation requires two steps. Therefore. Incident I. 1. The material also might not ignite at all. (Note that for simplicity only two wind directions are assumed for the outcomes cases). all persons within 100 meters of the explosion center are 30 . • Incident Outcome Case IIA (explosion) – the explosion is centered at the center point of the facility. Estimation of the effects (impact) that this physical concentration of material or energy has on people. all persons within 200 meters of the explosion center are killed (probability of fatality = 1. Estimation of a physical concentration of material or energy at each location starting from the point of origin of the incident: radiant heat from a fire. concentration of a toxic material in the atmosphere 2. The application of consequence and impact models to facility X yields simple impact zone estimates for the identified incident outcome cases: • Incident Outcome Case I (explosion) – the explosion is centered at the center point of the facility. Event Trees for the Incidents I and II The Incident II. has several possible outcomes (jet fire. all persons beyond this distance are unaffected (probability of fatality = 0). and the consequence and effects are unaffected by the weather. These are referred to as potential accident scenarios or as incident outcomes. Some incident outcomes are further subdivided into incident outcome cases. vapor cloud explosion. overpressure from an explosion. for Incident I there is only one incident outcome and one incident outcome case. toxic cloud) and its event tree is also shown in fig 2. the explosion has only one possible outcome (the explosion).

the nature of the injury for both individual and societal risk calculations will be immediate fatality resulting from fire. IIB2 (toxic gas clouds) – all persons in a pie shaped segment of radius 400 meters downwind and 22. Therefore. or exposure to toxic vapors. Outside the impact zone. (per year) fi pf.50 width are killed (probability of fatality = 1. The total individual risk of fatality at each geographical location is then determined by adding the individual risk from all incident outcome case impact zones that impact that location (using Equation 1). • Incident Outcome Cases IIBI.y. This includes the nature of the injury to the individual.y = the total individual risk of fatality at geographical location x. with the individual risk values for each area listed in Table 2. ∑ IR i =1 n x. the likelihood of the injury occurring.y = where. y. The four impact zones from the four incidents are superimposed on a map of the region of the plant and its surroundings as shown in Figure 5. For example. Similar calculations for the other areas in Figure 5 give the results summarized in Table 2. 31 .i IRx.” In this example.y. Individual Risk Estimation Individual risk is defined as “The risk to a person in the vicinity of a hazard. the wind blows from the Northeast 50% of the time.y from incident outcome case i (probability of fatality per year) n = the total number of incident outcome cases considered in the analysis = frequency of incident outcome case i.y (probability of fatality per year) IRx.I = fi pf. The above considerations give the frequency estimates for the four incident outcome cases (shown in the event trees of Figure 4).(2) IRx. Individual Risk Contours Individual risk at any point is given by: IRx. fault and event tree methods are used for accident frequency estimation. We assume that the following values obtain for the 2 potential incidents on X: • Incident I – Frequency = 1 x 10-6 events per year • Incident II – Frequency = 3 x 10-6 events per year (for Incident II – Ignition Probability = 0. Figure 5 is an individual risk contour plot for this example problem.killed (probability of fatality = 1. the individual risk from that incident outcome case IRx.33) We further assume that annually.(1) .. Incident Frequency Analysis Reliability.i is equal to the frequency of that incident outcome case (Equation 2).0). explosion. within the impact zone for each incident outcome case..i = probability that incident outcome case I will result in a fatality at location x.y. and the time period over which the injury might occur.i = the individual risk of fatality at geographical location x. IRx. all persons beyond this distance are unaffected (probability of fatality = 0). and from the Southwest 50% of the time. Figure 3 illustrates these impact zone.i is zero.I . in the area labeled “C” in Figure 5.y. application of Equation 1 gives the results listed in Table 1.i = 1) throughout its geographical impact zone.0). all persons outside this area are unaffected (probability of fatality = 0). y Each incident outcome case has an equal impact (probability of fatality pf.

Circle Diameter = 200m Prob. of fatality = 1.1 x 10-5 IR = ∑ IRi = 32 .50 Prob. Angle = 22. of fatality = 0 Prob. For drawing this transect the necessary numbers are shown in tables 2 and 3.50 Prob. Angle = 22. Impact zones for Incident Outcome Cases Individual Risk Profile (Risk Transect) The individual risk profile (risk transect) is a graph showing the individual risk as a function of distance from the source of the risk in a particular direction.i IRi (per year) -6 I 10 1 10-6 IIB2 10-5 1 10-5 1.0 Circle Diameter = 100m Prob. of fatality = 0 Prob.0 Prob. Table 1 Individual Risk Calculation for Area “C” In Figure 5 Incident Outcome Case fi (per year) Pf. of fatality = 1.0 Triangle Height = 400m. of fatality = 0 Incident Outcome Case I Incident Outcome Case IIA Triangle Height = 400m.0 N E Prob. Figure 6 is the individual risk profile in the northeast direction. For the example problem. of fatality = 0 Incident Outcome Case IIB1 Incident Outcome Case IIB2 Fig 3. of fatality = 1. of fatality = 1.

f = 10 – 6/yr IIA – Ignition (Explosion) f = 10 – 6/yr IIB1 – Toxic Cloud to Southwest.5 Figure 4. = 0. f = 3x10 . Frequency (f) of Incident (final) Outcome Cases Incident Outcome Case IIB2 Effect Zone N E I E C G A Incident Outcome Case IIA Effect Zone Incident Outcome Case IIB1 Effect Zone B D F H J Incident Outcome Case I Effect Zone K Figure 5.33 II – Flammable Toxic Gas Release.6/yr IIB – No Ignition Toxic Cloud Prob. = 0. = 0. = 0. Individual Risk Contour Map 33 .67 Prob. f = 10 – 6/yr Prob.5 IIB2 – Toxic Cloud to Northeast.Incident Event Tree for Incident I I – Explosion f = 10 – 6/yr Incident Outcomes Incident Outcome Cases II – Explosion f = 10 – 6/yr Event Tree for Incident II IIA – Ignition Prob.

1 x 10-5 I.0 x 10-5 C I. IIA. IIB2 2.6 10 .5 10 . IIB2 2. IIB1 2. IIB2 1.Region (see Figure 5) A B C D E F G H I Distance (m) Table 2 Individual Risk Results Incidents Impacting Region Total Individual Risk of Fatality (per year) I.4 Individual Risk per year 10 . IIB2 1.1 x 10-5 A I.1 x 10-5 I. IIA.0 x 10-6 Table 3 Individual Risks in the Northeast Direction Region Incidents Impacting Total Individual Risk of Region Fatality (per year) Beyond E None 0 E IIB2 1.0 x 10-5 IIB1 1.1 x 10-5 I. IIA. IIB. B1 1. Individual Risk Transect in the Northeast direction 34 .7 100 200 300 400 500 Distance from the Plant in the Northeast (m) Figure 6.1 x 10-5 I.1 x 10-5 > 400 200 – 400 100 – 200 0 – 100 10 . IIA 1.1 x 10-5 I 1.1 x 105 IIB2 1.0 x 10-5 I. IIA 1.

In this example.i . For the example.(6) Curve: FN = Fi . The data in Table 5 can be plotted to give the societal risk F-N Curve in Figure 8. for all outcome cases i for which Ni ≥ N ∑ i where: FN = frequency of all incident outcome cases affecting N or more people.(5) ∑ x. The first step in generating an F-N Curve for the example problem is to calculate the number of fatalities resulting from each incident outcome case. per year . Because the impact zones for the example are simple. Societal risk measures are important for managing risk in a situation where there is a potential for accidents impacting more than one person.Figure 7 shows the location of people in the area surrounding the CP facility. and counting the number of people inside the impact zone. 35 . The data in Table 4 must then be put into cumulative frequency form to plot the F-N .. the adverse outcome considered is immediate fatality resulting from fire. Societal risk measures estimate both the potential size and likelihood of incidents with multiple adverse outcomes. y where Ni is the number of fatalities resulting from Incident Outcome Case i. F-N Curve A common measure of societal risk is the Frequency-Number (F-N) curve. Incident Outcome Case IIB2 Effect Zone N E 6 3 10 Incident Outcome Case IIA Effect Zone Incident Outcome Case IIB1 Effect Zone 2** 4** X 1** Incident Outcome Case I Effect Zone K Indicates X people at specified location ** Employees in on-site buildings Figure 7. explosion. or exposure to toxic vapors. per year Table 5 summarizes the cumulative frequency results. Fi = frequency of incident outcome case i. y Pf .i in Equation 5 equals 1. pf. this calculation can be done graphically by superimposing the impact zones from Figure 3 onto the population distribution in Figure 7. Table 4 summarizes the estimated number of fatalities for the four incident outcome cases. as determined by: Ni = Px . Population Distribution in and around CP Societal Risk Calculation Societal risk measures the risk to a group of people..

0 x 10-6 13 IIA 1.7 1 10 100 Number of Fatalities (N) Figure 8.Table 4 Estimated Numbers of Fatalities from Each Incident Outcome Case Incident Outcome Case Frequency Fi Estimated Number of Fatalities (per year) I 1.0 x 10-6 >13 + None 0 10 .1 x 10-5 6+ I.0 x 10-5 0 IIB1 1. IIB2 2. IIB1.4 Frequency of N or more Fatalities .x 10-5 13 + I 1. Societal Risk F-N Curve 36 . per year 10 .0 x 10-5 6 -5 IIB2 1. IIB1 1.0 x 10 3 Table 5 Cumulative Frequency Data for F-N Curve Number of Fatalities Incident Outcome Cases Total Frequency N Included FN (per year) 3+ I.6 10 .5 10 .

The purpose is to identify all possible deviations from the design conditions and to identify all the hazards associated with these deviations. less. other than 37 . The basic concept behind HAZOP studies is that processes work well when operating under design conditions. This requires the design engineer to review and suggest solutions to either remove the hazard or reduce its risk to an acceptable level. reaction. phase Commonly Used Guide Words no. as well as. Where deviations result in hazards. deviations from the process design conditions cause hazards and lead to operability problems. pressure. To enable a thorough examination. more. The application of an accepted set of guide words ensures that every conceivable deviation is considered. more. Each part is subjected to a number of questions based on a set of guidewords for the project. the plant is split into a number of parts. The guide words are normally applied in conjunction with a series of process parameters to arrive at a meaningful deviation. lower no. part of. The questions are formulated using a number of guide words to ensure a consistent and structured approach. level composition.HAZOP: An Introduction The Hazard and Operability study (HAZOP) systematically questions the design to discover how it can deviate from the design intention. actions are identified. The main process parameters with their commonly used guide words are as follows: Main Process Parameters flow temperature. sneak (leak) higher. reverse. These solutions are reviewed and accepted by the HAZOP team before implementation. less.

HAZARD AND OPERABILITY STUDY REORT Project title: Project number: P&ID number: Line number: Guide word Deviation Cause Consequences Sheet Date: Chairman: Study team: Safeguards Numbe r By Action Details Reply accepted of 38 .

possible runaway –do- Action required 1. 2. 2. 2.Exothermic Reactor: HAZOP CASE STUDY Item 1A Study node Cooling coils Process parameters Flow Deviations (guide words) No HAZOP Study applied to the Exothermic Reactor Possible causes Possible consequences 1. Control valve fails closed Plugged cooling coils 1. Loss of cooling. Select valve to fail open Install filter with maintenance procedure Install cooling water flow meter and low flow alarm Install 39 .

2. 1 Low water supply temperature 1. possible accumulation of unreacted materials 2. –do–do–do- 3. Loss of cooling. possible accumulation of unreacted materials 1. Install high flow alarm and/or cooling water high temp. None 1. None 1. See1A. 2. Cooling system capacity limited temp. 3. 2. High water supply temperature 1. No mixing. 1. Monomer feed continues. Stirrer motor malfunction Power failure 2B More 1. alarm 1. possible runaway –do–do1. possible runaway –do- 5. controller handles 1. None 1. Sooner than Later than Low High No 1.1 Instruct operators and update procedures See 1A-4 See 1A. Interlock between cooling flow and reactor feed 1. 2. 2. None. 4. 5. 3. 4. 2. resulting in high motor speed 1. None 1.3. 2. high temperature alarm to alert operator Check and monitor reliability of water service Place controller on critical instrumentation list See 1A. Partially plugged cooling line Partial water source failure Control valve fails to respond 1. 1. 1. reactant conc. 1C Low Reactor cools. 1. 5.2 See 1A. possible runaway on heating – do Diminished cooling. Not possible here 1. 2. Stirrer motor controller fails. Interlock with feed line 2. 1. increases 1. 2. 1. 1. possible runaway 1. 4. Monomer feed valve must fail closed on power loss 40 . builds. closing valve 3.2 Install check calve 1D 1E 1F As well as Part of Reverse 1G 1H 1I 1J 1K 2A Stirrer Temperature Agitation Other than. 2.2 Place valve on critical instrumentation list 1. 3. Cooling water service failure Controller fails and closes valve Air pressure fails. Contamination of water supply Covered under 1C Failure on water source resulting in backflow Backflow due to high backpressure Not considered possible Cooling normally started early Operator error 1. Temperature rises. Control valve fails open Controller fails and opens valve 1. 1B High 1.

F = events P = probability S = entire sample space n = number of samples in which event A occurred N = number of experiments m = number of components in series or in parallel Operations: ∪ : Operation of union ∩ : Operation of intersection A : Operation of complementation : Conditional P ( A ∪ B ) = P ( A) + P( B) − P( A ∩ B) Mutually exclusive events: P ( A ∩ B) = 0 Complementary events : P ( A) + P ( B) = 1 ⇒ P( A) + P( A) = 1 Conditional Probabilities: 41 . One must be familiar with this concept to be able to determine the value of the input parameters and to understand the results of a risk or reliability analysis. A.PROBABILITY THEORY IN CHEMICAL RISK ASSESSMENT The probability concept is the basis for a risk analysis or reliability analysis. B.

It follows that: For independent events: If events are dependent: Bayesian Estimation We know that in general: For any arbitrary event Ai Or: 42 .

(i.Let’s consider that one has a set events Ai which are exhaustive and mutually exclusive.. 43 . Updated failure data) P(Ai|B) : Probability of Ai after learning fact B. The equation is valid in general for any number of events A1. A2. prior to learning fact B.e. An. P(Ai) : Probability of Ai. Available generic data) P(B|Ai) : The probability of the observation.(i. is true..e. the following conditions hold: Using the previous relations: The last expression is Bayes’ theorem. A3 A1 AB A2 Considering Ai as class i. It is important to understand the meaning of the various terms in the Bayes expression: B: Collected plant-specific data. Exhaustive implies that every conceivable outcome is included in the prior distribution. given that A.….

The probability density function f(x) is given by: ‘t’ = dummy variable The properties of probability density functions make it possible to treat the areas under f(x) as probabilities: Mean.PROBABILITY DISTRIBUTIONS The cumulative distribution function F(x) is defined as the probability that the random variable x assumes values of less than or equal to the specific value x. median and mode of a distribution Mode (X) = the most preferred value of ‘x’ (the one with the maximum probability) 44 .

the values of X > μ are more widely dispersed than X < μ. 45 . Skewness ≡ E[( X − μ )3 ] > 0 .Median (Xm) = value of ‘X’ at which values of X above and below are equally probable. Skewness: Skewness ≡ E[( X − μ )3 ] = ∫ ( x − μ )3 f ( x)dx −∞ ∞ For a symmetric distribution: Skewness ≡ E[( X − μ )3 ] = 0 If.5 Mean (or Expectation): E( X ) = μ = ∫ ∞ +∞ −∞ xf ( x)dx In general the expectation of a function G(X) where ‘X’ is a random variable is: E[G ( X )] = ∫ G ( x) f ( x)dx −∞ Variance: Var ( X ) = σ 2 = ∫ ( x − μ ) 2 f ( x)dx −∞ +∞ Standard Deviation: σ ( X ) = Var ( X ) Coefficient of Variation: COV = δ ( X ) = σ ( X ) / μ ( X ) The COV gives the relative spread of ‘X’ around its mean value. Thus: F (Xm) = 0.

Skewness Coefficient: θ≡ E[( X − μ )3 ] σ3 Moment Generating Function: In general the nth moment of a probability distribution function is given by: E[( X n ] = ∫ x n f ( x)dx −∞ ∞ The moment generating function MGF of a random variable X ≡ GX ( s ) . Skewness ≡ E[( X − μ )3 ] < 0 . where‘s’ is an auxiliary (deterministic) variable.If. Thus. the values of X < μ are more widely dispersed than X > μ. where: GX ( s) ≡ E (e sX ) . GX ( s ) ≡ ∫ e sX f ( x)dx −∞ ∞ Now it follows that: ∞ ⎡ d {G ( s )} ⎤ ⎢ ds ⎥ = ∫−∞ xf ( x)dx = E ( X ) ⎣ ⎦ s =0 It may be shown that in general: ∞ ⎡ d n {G ( s )} ⎤ n n ⎢ ⎥ = ∫−∞ x f ( x)dx = E ( X ) n ⎣ ds ⎦ s =0 Binomial Distribution: p = probability of an event occurring Exponential Distribution: f ( x) = λ e − λ x F ( x) = 1 − e − λ x Normal Distribution: 46 .

Standard Normal Distribution: It follows that: μ z = 0. The relationship to normal distribution is as follows: if the stochastic variable ln(x) has a normal distribution. σ z = 1 The Normal Distribution Curve Lognormal Distribution: The lognormal distribution is used quite frequently in reliability and safety studies. The probability density function f(x) is given by: 47 . x has a lognormal distribution.

The Lognormal Distribution Curve Weibull distribution: β = shape parameter δ = lowest value life parameter θ= characteristic life Typical shapes of f(x) is shown below with δ = 0 48 .

The Poisson distribution is a discrete probability distribution and not a probability density distribution. 49 .Poisson Distribution: The Poisson distribution gives the probability of exactly x occurrences of a rare event (p ➝ 0) in a large number of trials (n ➝ infinity).

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