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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.

• •

1

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

2

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.

3

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

Propagation

Diminish

Termination

Increase

4

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

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

3 14.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 7.5 x 10-5 Construction 5 10 x 10-5 Sector 7 .

7 1.4 x 10-5 2.1 x 10-5 0.05 9.05 0.3 x 10-5 1. in a group of 1000 people for a working lifetime.6 0.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 4.2 1.e.6 x 10-5 8 x 10-5 7.2 0.8 4 3.4 x 10-5 2.1 x 10-5 FAR= number of fatalities in 108 working hours. 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 .. 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.

5 9 .(1) . M = gas molecular weight (kg/kg-mol). We define X. 1.1 to 1.67. pa = absolute downstream (atmospheric pressure (N/m2). A = hole area (m2).71 to 2.(2) ⎛ Ps ⎞ ⎛ γ +1 ⎞ If ⎜ ⎟ > ⎜ ⎟ ⎝ Pa ⎠crit ⎝ 2 ⎠ γ /( γ −1) Then the velocity if gas discharging from the leak is sonic.8). T = storage pressure (N/m2) and temperature (oK). Examples of Emission Source (Emergency Unplanned Releases) Gas discharge • Hole in equipment (pipe. PS. GV = Cd APS {(γ M / RT ) X }0.SECTION II: ACCIDENT EFFECT ANALYSIS Table below shows the various accident scenarios and consequences feasible in an industrial scenario.(4) Where GV = gas discharge rate (kg/s)..(3) Gas mass flow rate through an orifice is given by: . dimensionless) Typical values of γ range from 1. upstream pressures over ~ 1.. In the above formula where ps = absolute upstream (storage pressure (N/m2). R = gas constant (8314 J/kg-mol /oK). 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.. GAS DISCHARGE γ /( γ −1) ⎛ γ +1 ⎞ We define a ratio r = ⎜ ⎟ ⎝ 2 ⎠ . Cd = discharge coefficient (~ 0. γ = gas specific heat ratio (Cp/Cv.05. Thus for releases of most industrial gases to atmosphere.9 bar absolute will result in sonic flow. which give ‘r’ values of 1.. 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..g. such that: X =( 2 (γ +1) /(γ −1) ) γ +1 .

74.1 m)..0/1.01) 2 4 (490) 2(10)(10 5 ) + 2(9.0. A= discharge hole area (m2). then the following equation is recommended: .. 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.. Therefore use the liquid discharge model.15 × 44 /(8314 × 298)}(0.(6) GLV = [AΛ/(ρg-1. X =( Thus X= 0. Data: Propane heat capacity ratio = 1.0 = 5.(5) + 2 gH ⎟ ρl ⎝ ⎠ Where GL = liquid mass emission rate (kg/s). p = pvp) and equilibrium two-phase choked flow is established during release through a severed pipeline (i. Cd = discharge coefficient (dimensionless).5 kg/s 3. the discharge will initially be liquid. sharp edged orifices is 0. the discharge must be as a pure gas. Therefore use a gas discharge equation.Example: Calculate the discharge rate of propane through a 10-mm hole for conditions of 25oC and 4 barg (5 bara).3 barg Since the total pressure is less than the vapor pressure of propane.e. Data: Propane density = 490 kg/m3.3 barg At P = 10 barg.e.6 – 0.64. p = liquid storage pressure (N/m2 absolute).e. LIQUID DISCHARGES Discharge of pure (i. Example: Calculate the discharge of propane from a tank through a 10-mm hole at 10 barg. the flow is sonic. Propane vapor pressure 25oC = 8. Here Ps /Pa = 5.. H = height of liquid above hole (m) The discharge coefficient for fully turbulent discharges from small. Thus.15. which exceeds r = 1. g = acceleration of gravity (9.8)(2) 490 = 1.35 2 (γ +1) /(γ −1) ) γ +1 GV = (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 .81 m/s2). pa = downstream (ambient) pressure (N/m2 absolute).01) 2 / 4}(5 ×105 )[{1.. 25oC with 2 m liquid head.5 = 0.8){π (0. nonflashing) liquids through a sharp-edged orifice/nozzle is given by: ⎛ 2( p − pa ) ⎞ GL = CdAρl ⎜ .61) π (0.09kg / s 2. TWO-PHASE FLOW If the liquid is stored at saturation (i.35)]0. ρl = liquid density (kg/m3). pipe length > 0. Propane vapor pressure 25oC = 8.

and the liquid does not have time to flash within the hole.4 x 105 J/kg Hence FV = 2400 ⎜ ⎛ 130 − 69 ⎞ ⎟ = 0. The result will only be valid for liquids stored at a pressure higher than the saturation vapor pressure.(7) x < p(ρg-1.65 200 0. then a more complicated numerical model is necessary to calculate the emission rate. This fraction is approximated from the thermodynamic relationship ΔT = (T .43 ⎝ 340000 ⎠ Flashing liquids escaping through holes and pipes require very special consideration since two-phase flow conditions may be present. where Lp and D are pipe length and diameter..75 100 0.55 400 4.. a fraction. FRACTION FLASHED FROM LIQUID DISCHARGE For superheated liquids (i. Data Cp = average liquid heat capacity (range T to Tb) ~2400 J/kg/oK T = operating temperature (i. Several special cases need consideration.e. Suggested values for F are given in Table 2. that accounts for frictional losses. If the fluid path length of the release is very short (through a hole in a thin-walled container). f. Example: Leak of hexane from a pressurized pipeline at 5 bar.(9) 11 . in Eq. Table 2: Variation of Factor F with Ratio Lp/D Lp/D F 1 0 0.e boiling point at 5 bar = 130oC) Tb = atmospheric boiling point (69oC) Hvap = latent heat of vaporization at Tb = 3. GLV. respectively. With this assumption the mass flow rate is given by Gm = ACo 2ρ f gc (P . of the liquid emission is "flashed" to vapor as the pressure is reduced to ambient.This equation applies only if the following condition is met: . If the fluid path length through the release is greater than 10 cm (through a pipe or thick-walled container).P sat ) .(8) FV = CpΔT/Hvap Where Ts is process line/vessel temperature and Tb is normal boiling point temperature. F. The equations describing incompressible fluid flow through holes apply. the fluid flashes external to the hole. Hvap the heat of vapourization at normal pressure..Tb) oK .. Frictional losses for saturated liquids For long pipe lengths the mass emission rate. equilibrium flashing conditions are achieved and the flow is choked.85 50 0. A good approximation is to assume a choked pressure equal to the saturation vapor pressure of the flashing liquid. If this condition is not met.ρl-1)(TsCpl)/Λ2 Where x is the weight fraction of vapor after depressurizing to atmospheric pressure. stored at temperature above the normal boiling point). nonequilibrium conditions exist.(6) should be multiplied by a factor.

0(kg m/s 2 ) / N 3 J/kg K ( 298 K) (1N m/J) ) GLV = 0.Example Liquid ammonia is stored in a tank at 24oC and a pressure of 1.0945 m) 2 / 4 x 2(603 kg/m 3 ) [1(kg m/s 2 ) / N] (1. ρf is the density of the liquid (mass/volume). For this case the choked. Co is the discharge coefficient (unitless). P = Psat. Equation 10 is used.14)(0. P is the pressure within the tank. Cp = 2. Determine the mass flow rate through the leak. For liquids stored at their saturation vapor pressure. Example: Propylene is stored at 25oC in a tank at its saturation pressure. A 1-cm diameter hole develops in the tank. The saturation vapor pressure of liquid ammonia at this temperature is 0.6 kg/s Where.774 kg/s 12 .968 x 10 6 ) (N / m 2 ) Gm = 97.34 x 105 J/kg. At these conditions. These aerosol droplets are readily entrained by the wind and transported away from the release site. Gm = ACo 2ρ f gc (P .P sat ) = (0. A is the area of the release. two-phase mass flow rate is given by: ΔH v A g c GLV = .34 x 105 J/kg) (1 N m/J) Cp T 0. GLV = ( ) 2 = 7. Estimate the mass flow rate through the hole.18 x 10 1.18 x 103 J/kg K Equation 10 applies to this case.61.61) (3.15 x 106 Pa.968 x 106 Pa and its density is 603 kg/m3. ΔHv = 3. Solution.85 x 10-5 m2 ΔH v A v fg gc 7.042 m3/kg.(10) v fg C pT Small droplets of liquid also form in a jet of flashing vapor.042 m 3 / kg x ( ( ) ) (2.0945 m forms in the tank. A leak of diameter 0.. Equilibrium flashing conditions can be assumed. and Psat is the saturation vapor pressure of the flashing liquid at ambient temperature. Equation 9 applies for the case of equilibrium flashing conditions. psat = 1.14 ) 1 x 10 . vfg = 0.85 x 10 -5 m 2 = (3. Assume a discharge coefficient of 0.4 x 106 Pa. The area of the leak is πd 2 (3. for propylene.2 m = A= 4 4 Using Equation 54. The assumption that the quantity of droplets formed is equal to the amount of material flashed is frequently made.4 x10 6 − 0.

.(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. Ge = kgApvpM/R*Tp .(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. then an empirical formula for slowly evaporating pools can be applied. given by the formula Kg = DmNsh/d ... SLOWLY EVAPORATING POOL In many cases the hazardous material does not evaporate before it hits the ground surface.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. B. If the rate of evaporation is light to moderate (i. slightly conditions. given by the correlation NSh = 0. the pool temperature is within a few degrees of ambient and the liquid does not boil). neutral conditions. and the liquid is well mixed. Extremely unstable conditions. slightly unstable conditions. Plumes refer to with the travel time (time for cloud to reach location of 13 . TABLE 3 Pasquill Stability Meteorological Conditionsa. The dispersion phenomenon depends on whether the gas is lighter or heavier than air.5. F.e. 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. moderately unstable conditions.037(km/Dm)1/3[(ud/km)0.8-15200] .. moderately conditions.(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). 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. C. Once released. they will be dispersed by atmospheric conditions. D.

91 D 0.89 F 0.. z .92 0. 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.093x0. σz = dispersion coefficients (m). FORMULA FOR INSTANTANEOUS PUFF EMISSIONS: ⎡ M y2 −( x − ut ) 2 −( z − H ) 2 −( z + H ) 2 ⎤ C ( x.88 0.10x 0.135x0. t = time elapsed after release (s) Puff emissions have different spreading characteristics from continuous plumes and different dispersion coefficients (σy.(14) Where x.z = distance from source.04x0.53x0.05x0.15x0.90 0.interest) or sampling (or averaging) time (normally 10 min).06x 0.493x A 0.087x1.60x0.057x0.92 A 0.63 14 .09x 0.34x0. Use of such formulas allow for easier computerization of the method.112x0.10x0. M = amount released instantaneously (kg).95 0.(15) Where.75 B 0. t ) = exp{ ]}⎥ − 2 }{[ exp + exp ⎢ 2 (2π )3/ 2 σ xσ yσ z ⎢ 2σ x 2σ y 2σ z2 2σ z2 ⎥ ⎣ ⎦ . Also because of a lack of data. y = crosswind.195x 0. z = vertical) c = concentration (kg/m3) at location x.90 C 0.65 0.82 F 0.92 D 0.128x0.082x0.73 0. these differ slightly. σy. y . m (x = downwind.92 C 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. The basis for the PasquillGifford model is Gaussian dispersion in both the horizontal and vertical axes.337x 0. H = height of source above ground level plus plume rise (m).91 E 0. GV = vapour emission rate (kg/s). 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. 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 ⎦ ⎣ ⎦ .85 0.10 0. function of distance downwind.02x 0.y.067x0.90 0. σz).14x0. it is often assumed σx = σy.18x0.88 B 0.71 0.92 0.70 E 0. y. z.

for fires the consequences of concern are thermal radiation effects. The release occurs at 2 m. 10 m crosswind.90 = 9. R = 0.4) 2 ⎦ G RTa (0. The following accident scenarios are considered: • Unconfined Vapor Cloud Explosions and Flash Fires • BLEVE and Fireball • Pool Fire and Jet Fires 15 .4) 2 2(5.093x0. σz = 0. within buildings or vessels) or an unconfined state (i. An explosion can be thought of as a rapid equilibrium of a high-pressure gas with the environment. 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.. 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.4 m Concentration in kg/m3 can be found from Equation (14): C= = 2.3 kg/s located 2 m above ground level at a place 120 m downwind. the plume is constrained by ground level. so the mean height for wind estimation is selected as 2 m. The leak rate is small.5) 2 ⎦ ⎣ 2(5. Mo = 71. Ta = 20oC (293oK). Data: Assume ground roughness is equivalent to urban conditions.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)0.3 m/s Dispersion coefficients for D stability evaluated at x = 120 m (using table above) σy = 0.3) ⎣ 2(9.128x0. Weather conditions correspond to D stability.e. Stability class = D. Gas constant. thus dispersion will rapidly ensure that the dense gas behaviour zone is negligible and a Gaussian model is adequate. assume that the plume is at near ambient temperature (Ta).Example on Plume Discharge: Calculate the concentration of chlorine from a source of 0. This equilibrium must be rapid enough that the energy contained in the high-pressure gas is dissipated as a shock wave. Chlorine molecular weight. The consequences of concern for explosions in general are shock wave overpressure effects and projectile effects.3 = + exp exp exp ⎢ ⎥⎢ ⎥ 2π (9. unconfined vapor cloud explosions or UVCE).5)(5. When explosions arise from a combustion reaction usually the thermal radiation effects are ignored because the shock wave effects will predominate. 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 ⎤ 0.85 = 5. pressure p = 1 atm abs. These latter reactions can occur both in a confined state (i. and 2 m height.5 m.4)(3.e.. Ambient temperature. 5 m/s wind (at 10 m height).72 x 10-4 kg/m3 To convert this into ppm (vol).082)(293) x 106 = (2.25 = 3.72 x 10-4) x 106 = 92 ppm PM o (1)(71) 2.

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

. 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.825 M0. x = path length. Assume an explosion yield (η) = 0. Data: Mass = 10 tons. 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.(19) Center height of fireball (m) HBLEVE = 0.26 . weakening the container and leading to sudden shell rupture.Example Using the TNT equivalent model.3 Dmax . Converting scaled distance to real distance: RG = ZG W1/3 = 7 m/kg1/3 x (4530 kg)1/3 = 113 m 0.(23) where τ = atmospheric transmissivity (fraction energy transmitted: 0 to 1).02(Pwx)-0. calculate the distance to 5 psi overpressure (equivalent to heavy building damage) of an UVCE of 10 short tons of propane. A pressure relief valve does not protect against this mode of the failure. N/m2). This causes a reduction in radiation received at target locations.(20) Initial ground level hemisphere diameter (m) Dinitial = 1.(21) where M = initial mass of flammable liquid (kg). 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. that a BLEVE can occur due to any mechanism that results in the sudden failure of containment allowing a superheated liquid to flash. This is sufficient to generate a pressure wave and fragments. The radiation received by a target (for the duration of the BLEVE incident) is given by QR = τEF21 .75 Dmax .05 x 10. however. distance from flame surface to target (m) 17 .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. Assume EcTNT = 4650 kJ/kg From Equation (16). E = surface emitted flux (kW/m2) F21= view factor (dimensionless) The atmospheric transmissivity τ. It should be noted. Thermal radiation is absorbed and scattered by the atmosphere. If the released liquid is flammable. typically increasing its volume over 200 times.(22) where QR = radiation received by a black body target (kW/m2) τ = transmissivity (dimensionless).05.325 .. W = ηME c E cTNT = 0. Useful formulas for BLEVE physical parameters are Peak fireball diameter (m) Dmax = 6. The correlation formula that accounts for humidity is: τ = 2. the scaled distance (ZG) to 5 psi (Pso m/kg1/3. a fireball may result.(18) Fireball duration (s) tBLEVE = 0.09 ... Lower heat of combustion of propane (Ec) = 46350 kJ/kg..000 x 46350 4650 = = 4530 kg From Figure above.48 M0. is an important factor.. Pw = water partial pressure (Pascals.

Dmax = peak fireball diameter (m). the maximum diameter is reached when the product of burning rate and surface area equals the 18 . M = mass of LPG in BLEVE (kg). D2 .(25) F21 = 2 4r where F21 = view factor between sphere and target surface. Frad MH c . Frad = radiation fraction. rather than for community risk.g. typically 0. on an infinite flat plane. They tend to be localized in effect and are mainly of concern in establishing the potential for domino effects and employee safety zones.25-0. Pool fire models have been applied to LNG spills as well as more common flammable materials. 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.4.. Pool Size: In most cases. 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. unlike those for dispersion and UVCE. as the latter requires the flame temperature. pool size is fixed by the size of release and by local physical barriers (e. rather than the Stefan-Boltzmann equation. dikes. Hc = heat of combustion (kJ/kg). Pool Fire Models Burning Rate: Large pool fires burn at a constant vertical rate. sloped drainage areas). This fraction is typically 0. E. Pool and jet fire models. The surface heat flux is based on the radiative fraction of the total heat of combustion. Typical values for hydrocarbons are in the range 0.. a geometric view factor for a sphere to a surface normal to the sphere (not the horizontal or vertical components) should be used. TBLEVE= fireball duration (s) As the effects of a BLEVE mainly relate to human injury. characteristic for the material. For a continuous leak.05 kg/m2s (gasoline) to 0.Thermal radiation is usually calculated using surface emitted flux.40.(24) E= π ( Dmax ) 2 t BLEVE where E = surface emitted flux (kW/m2). The most common application of jet fire models is the specification of exclusion zones around flares..25-0.12 (LPG). Typical heat fluxes in BLEVEs (200-350 kW/m2) are much higher than in pool fires as the flame is not smoky.

FP = 1 1 = = 8. QR can be estimated.0 x 106 = 5. x = distance from point source to target (m). where dikes lead to square or rectangular shapes. Flame Height: Many observations of pool fires show that there is an approximate ratio of flame height to diameter. Weather conditions are no wind. kJ/kg.15-0.. τ = atmospheric transmissivity (dimensionless). m2 Q = 0. QR = total heat radiated (kW). Typical values of H/D are in the range 2-3. Data: burning rate = 013 kg/m2s.02(2320x100)-0.700 kJ/kg x π (0.35 x 2. 20oC and 50% relative humidity. 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. The radiation fraction of total combustion power is often quoted in the range 0. heat of combustion = 43.09 = 0. an equivalent diameter may be used. 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: . At closer distances.8 x 106 kW = 9. QR = 0. Surface Emitted Power: LPG and LNG fires radiate up to 250 kW/m2.35. This must be applied to the total heat output. Circular pools are normally assumed.700 kJ/kg.13 kg/m2s x 43. Received Thermal Flux: The received thermal flux (on a target) from a pool fire is given by Qx = τQRFp ./5 x 25)2 m2 = 2. 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. but smoke obscuration often reduces this to 20-60 kW/m2. as this radiant fraction is high for smoky pool fires) then the radiant heat.35 (conservative.8 x 106 kW Assume radiant fraction for hydrocarbon fires = 0.66 x 0. more rigorous formulas or tables are used.(26) Fp = 1/ 4π x 2 -2 Where Fp = point source view factor (m ). 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.02(Pwx)-0. View factors are discussed in texts on thermal radiation.98 x 106 Kw x 8.0 x 106 m-2 2 2 4πx 4π 100 Using Equation (23) for a distance of 100 m: τ = 2.(27) 2 Where Qx = thermal radiation received at distance x (kW/m ). Geometric View Factor: The thermal radiation received at a target location is determined by the geometric view factor (ignoring atmospheric absorption).09 = 2. Upper values for other hydrocarbon pool fires lie in the range 110-170 kW/m2. not to the flux per unit area.8 x 105 kW.Example: Determine the thermal flux received at a distance of 100 m from a pool fire contained in a 25-m-diameter tank dike. Fp = point source view factor (m-2) 19 . Ec = heat of combustion.8 x 106 kJ/s = 2.2 kW/m2 leakage rate.. A = pool area. kg/m2s.

77 3.9 t0..9 t0..50 = side-on hazard range to 50% lethality (m.53 4. but subject to 1< m< 3000 kg/s).50 = 1. V.90 4.64 4. but subject to r>W).33 4.85 4.. Example: Determine the 50% lethality range for a pressurized release of LPG @ 25 kg/s lasting for 100s. The dimensions of the torch flame which is assumed to be conical. the side-on hazard zone for 50% lenthality is 54 m from the jet flame centerline.80 4.25 3.67 4...92 3.52 3.75 4.82 4.( 32) 9 3.29 4.45 3.72 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).59 4.(30) Rs.92 4. The probit variable Y is computed from the following equation: Probit = Y = k1 + k2 ln V % 0 10 20 30 40 .08 4.87 4.42 4.12 4. W = jet flame conical half-width at flame tip (m).25L .36 4.56 4.87 3. t = exposure time (s.16 4.23 4.82 3.01 4. For single exposures. The causative factor represents the dose.5 W = 0.50 = 1.47 = 54 m Thus.72 3. rs.66 4. are given by (for LPG): . Table 7 shows a variety of probit equations for a number of different types of exposures.36 3. Here dose refers to the intensity of accident outcome (air-borne concentration of a toxic material.61 4. 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. From Equations (28)-(30) the jet flame dimensions are determined: L = 9. This relationship is tabulated in Table 6. Standard curve fitting techniques are used to determine the best fit straight line.47 where L = length of torch flame (m).4 m0.95 .25L = 11 m (half width) rs.48 4.67 2.Jet Fire Models: Jet fire modeling is not as well developed as for pool fires.59 3.9x1000.5 = 91 x 250.4 x 250. the probit (probit = probability unit) method is particularly suited.50 4.45 4.(31) P= exp ⎜ − ⎟du ∫ ⎝ 2⎠ 2π −∞ Equation A provides a relationship between the probability P and the probit variable Y.19 4.5 = 45 m W = 0. but subject to 10<t<300s)The end-on hazard zone is 85% of the side-on hazard zone.97 20 Table 6: The Transformation from Percentages to Probits 0 1 2 3 4 5 6 7 8 -2. while response implies the human/property damage caused by the accident. but several reviews have been published.47 = 1.96 4.77 4.26 4.39 4.1 m0.(28) L = 9.12 3.1 m0.(29) .4 m0. M = LPG release rate (kg/sec. ESTIMATION OF EFFECTS OF ACCIDENTS: PROBIT ANALYSIS Many methods exist for representing the response-dose curve.95 3.69 4.05 4.

8 2. For a probit less than 2.88 0.33 5.5 7.33 0.71 6.995 (or 99.58 4.67.88 5.8 7.74 6.41 5.28 5.1 7.05 5.55 0.29 0. the probability of fatality is 50%.36 5. For a probit of 7.00 5.09. Ie= effective radiation intensity received by target (W/m2) Explosion: Deaths from lung hemorrhage po -77.10 5.04 6.13 6.95 the probability is 0.92 ln (602 x 60) = 5.47 5.67 6.05 0.1 6.13 5.Using table 3. For a probability of 0.0 7.44 5. For a probability of 0.50 60 70 80 90 % 99 5.64 0.18 7.05 (or 5%) 5.84 3.7 7.72 2.9 2.15 5.99 6.6 7. the causative variable V is representative of the magnitude of the exposure.95 6.09 Examples: 1.3 7. the probit is 5.8 (or 80%).31 5.52 5.58 5.03 5. the probability is 0. For a probit of 3. Table 7: Probit correlations for exposures.39 5.92 ln (C2t) = – 8.92 6.51 5.2%) 7.91 po Eardrum ruptures -15.9 8.55 5.08 6.46 5.4 7.6 1. 8.2 7.84 6.33 5.48 (or 48%) 6.50 5. the probit is 7.48 0.93 o p Structural damage -23. the probit is 3.36 the probability is 0.58 5.36 the probability is 0.01 .41 0. 21 .18 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 5.28 0.41 5.1 2.56 teIe4/3/104 te= effective time of exposure (s).23 5. For a probability of 0.992 (or 99.29 + 0.20 5. For a probit of 4.75 5. the probability is 100%.88 6.92 C2T C= concentration (ppm).08 5.77 6. For a probit more than 8.75 0.65 5.61 5.81 6.25 5.37 5.92 po Glass breakage -18.23 7.5%).34 0.29 + 0. Type of injury or damage Causative Probit variable Parameters V k1 k2 Fire: Burn deaths from fire -14. Ychlorine = – 8.79 o 2 p = peak overpressure (N/m ) Toxic release: Chlorine deaths -8.64 5.1 (or 10%) .

is: Yburn deaths = – 14. based on .(33) nuclear explosion data.Table 9 Thermal Radiation Impact Criteria Criterion Level (kW/m2) 40 20 12. 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. 22 .1 + 6.91 ln 34455 = – 4.7) x 101300 N/m2 = 34455 N/m2 Hence Y = – 77. 5.1 + 6. 15psi overpressure is the approximate threshold for fatality.56 ln tI 4/ 3 /10000 Where Pr = probit.5 Likely Effects at Criterion Level Immediate fatality. t = duration of exposure (sec).9 + 2.68 The probability of fatality is ~ 1%. leading to fatality unless rescue is effected quickly. Limiting flux for secondary fires.91 ln p0 Now p0 = 5 psi = (5/14. Thus. Incapacitation.1 + 6. Example: What is chance of death from lung hemorrhage for an exposure to 5 psi blast pressure? From Table 7 Yfatality from hemorrhage = – 77. A probit model to estimate injury levels for a given thermal dose from pool and flash fires.9 (From table 6. I = thermal radiation intensity (W/m2) Table 8 Explosion Impact Criteria Explosion Overpressure Effect • • 35 m bar (0. complete demolition of houses Relatively high blast overpressures (>15 psig) are necessary to produce fatality (primarily due to lung hemorrhage). also.1 Threshold value below which escape should always be possible.91 ln (103365) = 2. Extreme pain within 20 seconds and movement to shelter is instinctive. but can be repaired • Probability of injury is 10%.. The probit method has found less use for thermal injury than it has for toxic effects. the chance is negligible) If overpressure is 15 psi (1 atm): Y = – 77.5 psi) 90% glass breakage No fatality and very low probability of injury 70 mbar (1 psi) • Internal partitions & joinery damaged.

Determine the thermal flux necessary to cause 50% fatalities for 10 and 100 seconds of exposure. P. For 50% fatality.(2) P(t) = 1 .. 23 . The complement of the reliability is called the failure probability (or sometimes the unreliability).56] / t ⎤ ⎣ ⎦ 2 3/ 4 . Equation (33) can be rearranged to solve for the thermal radiation intensity I: For t = 10 s.. I = ⎡104 e[(Pr + 14.9 + 2. A fixed criterion. 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 = 61 kW/m . . Yburn deaths = –14. may be inappropriate for such incidents.(3) The area under the plot of complete failure density function is unity. Data is collected on the failure rate of a particular hardware component.56 ln ⎡ 20(20.e-λt The failure density function f(t) is defined as: f(t) = dP(t) = λ e−λ t dt ∞ .9 + 2. when t the reliability goes to 0.(4) Equations 1through 5 are only valid for a constant failure rate. For t = 100 s. λ. suitable for prolonged exposures. Using the probit method. The probability the component will not fail during the time interval (0. i. This is called the average failure rate and is represented by λ with units of faults/time. With adequate data it can be shown that.56 ln tI 4 / 3 /10000 = – 14. 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).R(t) = 1 .0 (Table 4). the component fails after a certain period of time. I = 11 kW/m2 This example demonstrates the importance of duration of exposure. R is the reliability. ∫ f(t)dt = 1 . t) is given by: . Between these two periods. especially for short duration incidents such as BLEVEs (on the order of 10-20s). on the average.00 ⎣ ⎦ Hence using table 6 the chance of fatality is ~ 2 % 2.Example 1. 000) 4 / 3 /10000 ⎤ = 3. Pr = 5.9) / 2. Many components exhibit a typical "bathtub" failure rates... The overall probability of a failure in a process is dependent on the nature of this interaction. What is the chance of human fatality for 20s exposure to 20kW/m2? Using Eq 33 (or table 7).e. 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. Equation 1 assumes a constant failure rate.(1) R(t) = e-λt where. the failure rate is reasonably constant and Equation 2 through 4 are valid. and is given by .

(7) .. For series components the overall system process reliability.044 Strip chart recorder 0.44 FAULT TREES Fault trees are a deductive method for identifying ways in which hazards can lead to accidents.13 Alarm Indicator lamp 0. in that. Rsys = 1 - ∏ (1 .52 Thermometer 0. materials of construction.Interaction between Process Units Accidents in chemical plants are usually the result of a complicated interaction between a number of process components.Pi ) Failure rate data for a number of typical process components are provided in Table 1.41 Pressure relief valve 0.∏ (1 . design of the component.14 Solenoid valve 0. These values depend on manufacturing practices employed by manufacturer. Table 1 Failure Rate Data for various selected process components Instrument Faults/year Controller 0. In such cases the overall process failure probability is computed from the individual component failure probabilities.60 Hand valve 0. and works backwards towards the various scenarios or events that can cause the accident. These are average values determined at a typical chemical process facility. they are connected in a "Series" structure within a system.027 Valve positioner 0. is: Rsys = ∏R i =1 n i =1 n i . Process components also interact in series.22 Thermocouple 0.022 Pressure switch 0.(5) where n is the total number of components and Pi is the failure probability of each. Rsys. or top event.R ) i i =1 n .(8) Psys = 1..70 Pressure gauge 1. Process components interact in two different ways. the physico-chemical environment in which the component functions etc.29 Control valve 0.42 Stepper motor 0.044 Level measurement meter (liquids) 1.. The approach starts with a well-defined accident. In such a case the system unreliability is: Psys = ∏P i =1 n i .(6) Where Ri is the reliability of an individual process component. Events in fault 24 .. In some cases. a process failure requires the simultaneous failure of a number of components operating in a "parallel" mode.

a number of additional logic functions are needed to construct a fault tree. OR gate is used for describing events that need occur alone to result in output event. Exothermic Reactor System 25 . The AND logic gate is used for describing processes that interact in parallel. and environmental abnormities. It can also include software failure.tree are not restricted to hardware failures. human error. 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. For reasonably complex chemical processes.

The third safety function is the operator re-establishing the coolant flow by correcting the problem within time. This system features a high temperature alarm that has been installed to warn the operator of a high temperature within the reactor. Four safety functions are identified. The operator may also notice the high temperature on his own during normal inspection. The second safety function is the operator noticing the high reactor temperature during normal inspection. 26 . These safety systems may in turn either fail or succeed in their operation. various safety systems come into operation in order to prevent the accident from propagating. When an accident occurs in a plant. The event tree for a loss of coolant initiating event is shown in the next figure. The first safety function is the high temperature alarm.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 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. In constructing the event tree these safety functions are written across the page in the order in which they logically occur. The final safety feature is invoked by the operator performing an emergency shutdown of the reactor. Example: Consider the chemical reactor system shown in Figure below.

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

Event Tree for the Exothermic Reactor System 28 .

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

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

Outside the impact zone.I . Incident Frequency Analysis Reliability.y.y = where. • Incident Outcome Cases IIBI. fault and event tree methods are used for accident frequency estimation. the wind blows from the Northeast 50% of the time. ∑ IR i =1 n x. or exposure to toxic vapors. IRx.0). Similar calculations for the other areas in Figure 5 give the results summarized in Table 2.50 width are killed (probability of fatality = 1.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. 31 . the likelihood of the injury occurring.y = the total individual risk of fatality at geographical location x.i is zero.(1) .y. Figure 3 illustrates these impact zone.i is equal to the frequency of that incident outcome case (Equation 2). and from the Southwest 50% of the time. (per year) fi pf. with the individual risk values for each area listed in Table 2.. application of Equation 1 gives the results listed in Table 1.33) We further assume that annually.i IRx.killed (probability of fatality = 1. 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. Individual Risk Contours Individual risk at any point is given by: IRx.y (probability of fatality per year) IRx.. the nature of the injury for both individual and societal risk calculations will be immediate fatality resulting from fire. For example. in the area labeled “C” in Figure 5.y. The above considerations give the frequency estimates for the four incident outcome cases (shown in the event trees of Figure 4).i = probability that incident outcome case I will result in a fatality at location x. within the impact zone for each incident outcome case. the individual risk from that incident outcome case IRx. IIB2 (toxic gas clouds) – all persons in a pie shaped segment of radius 400 meters downwind and 22.i = the individual risk of fatality at geographical location x.I = fi pf.” In this example. This includes the nature of the injury to the individual. Individual Risk Estimation Individual risk is defined as “The risk to a person in the vicinity of a hazard.0). all persons beyond this distance are unaffected (probability of fatality = 0). y Each incident outcome case has an equal impact (probability of fatality pf. Therefore. explosion. 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).y. all persons outside this area are unaffected (probability of fatality = 0).i = 1) throughout its geographical impact zone. 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. y.(2) IRx. and the time period over which the injury might occur.

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

= 0. = 0.5 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. f = 10 – 6/yr Prob. = 0. = 0.67 Prob. f = 10 – 6/yr IIA – Ignition (Explosion) f = 10 – 6/yr IIB1 – Toxic Cloud to Southwest. Individual Risk Contour Map 33 . 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 5.5 Figure 4.6/yr IIB – No Ignition Toxic Cloud Prob.33 II – Flammable Toxic Gas Release.

1 x 10-5 I. IIB2 2.0 x 10-5 I. IIA.1 x 10-5 I 1.0 x 10-5 IIB1 1.1 x 10-5 I. Individual Risk Transect in the Northeast direction 34 .1 x 10-5 I. IIA.6 10 . B1 1. IIB1 2. IIA 1. IIB2 1.7 100 200 300 400 500 Distance from the Plant in the Northeast (m) Figure 6.0 x 10-5 C I. IIA.1 x 10-5 A I. IIB. IIB2 2.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.1 x 10-5 > 400 200 – 400 100 – 200 0 – 100 10 .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. IIB2 1.4 Individual Risk per year 10 .5 10 .1 x 10-5 I. IIA 1.1 x 105 IIB2 1.

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

IIB2 2.4 Frequency of N or more Fatalities .0 x 10-6 13 IIA 1. IIB1.0 x 10-6 >13 + None 0 10 .7 1 10 100 Number of Fatalities (N) Figure 8. Societal Risk F-N Curve 36 .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 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.0 x 10-5 0 IIB1 1.6 10 .5 10 . IIB1 1.x 10-5 13 + I 1.0 x 10-5 6 -5 IIB2 1.1 x 10-5 6+ I. per year 10 .

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

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 .

Control valve fails closed Plugged cooling coils 1. 2. 2. Select valve to fail open Install filter with maintenance procedure Install cooling water flow meter and low flow alarm Install 39 .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. 2. Loss of cooling. possible runaway –do- Action required 1.

3. None 1. None. possible runaway –do- 5. Monomer feed valve must fail closed on power loss 40 . 2. 2. Temperature rises. 3. 1. Interlock with feed line 2. high temperature alarm to alert operator Check and monitor reliability of water service Place controller on critical instrumentation list See 1A. 2. 4. 2. 2. controller handles 1. possible runaway –do–do1. 1. Loss of cooling. Cooling system capacity limited temp. Monomer feed continues. 2. 4. 1.3. 2. 1. 1 Low water supply temperature 1. None 1. 4. 3. Control valve fails open Controller fails and opens valve 1. reactant conc.2 Place valve on critical instrumentation list 1. 1B High 1. See1A. 5. possible accumulation of unreacted materials 1. 5. 1. 1C Low Reactor cools. Sooner than Later than Low High No 1. possible runaway 1. alarm 1. Interlock between cooling flow and reactor feed 1.1 Instruct operators and update procedures See 1A-4 See 1A. 1. Partially plugged cooling line Partial water source failure Control valve fails to respond 1. increases 1. None 1. possible accumulation of unreacted materials 2. 2. possible runaway on heating – do Diminished cooling. Cooling water service failure Controller fails and closes valve Air pressure fails. High water supply temperature 1. 2. No mixing. Stirrer motor malfunction Power failure 2B More 1. 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. Install high flow alarm and/or cooling water high temp. None 1.2 Install check calve 1D 1E 1F As well as Part of Reverse 1G 1H 1I 1J 1K 2A Stirrer Temperature Agitation Other than. closing valve 3. Stirrer motor controller fails. 2. resulting in high motor speed 1. Not possible here 1. builds. –do–do–do- 3.2 See 1A. 1.

A. B. 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.PROBABILITY THEORY IN CHEMICAL RISK ASSESSMENT The probability concept is the basis for a risk analysis or reliability analysis.

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

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

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. median and mode of a distribution Mode (X) = the most preferred value of ‘x’ (the one with the maximum probability) 44 .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.

Thus: F (Xm) = 0. 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. Skewness ≡ E[( X − μ )3 ] > 0 . the values of X > μ are more widely dispersed than X < μ.Median (Xm) = value of ‘X’ at which values of X above and below are equally probable. 45 .

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 ) . Thus.If. where: GX ( s) ≡ E (e sX ) . where‘s’ is an auxiliary (deterministic) variable. Skewness ≡ E[( X − μ )3 ] < 0 . the values of X < μ are more widely dispersed than X > μ. 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 .

x has a lognormal distribution.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 .

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.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). 49 .

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