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# CHEMICAL PROCESS SAFETY: ANALYSIS & MANAGEMENT

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.

• •

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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

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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.

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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

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

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

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.3 14. 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 .

6 x 10-5 8 x 10-5 7. i.1 x 10-5 FAR= number of fatalities in 108 working hours.4 x 10-5 2.4 x 10-5 2. 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.6 0.2 1.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 4.05 9.05 0. 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 .7 1. in a group of 1000 people for a working lifetime.e.1 x 10-5 0.8 4 3.3 x 10-5 1.2 x 10-5 0.2 0..

. GAS DISCHARGE γ /( γ −1) ⎛ γ +1 ⎞ We define a ratio r = ⎜ ⎟ ⎝ 2 ⎠ . dimensionless) Typical values of γ range from 1. GV = Cd APS {(γ M / RT ) X }0. upstream pressures over ~ 1.(2) ⎛ Ps ⎞ ⎛ γ +1 ⎞ If ⎜ ⎟ > ⎜ ⎟ ⎝ Pa ⎠crit ⎝ 2 ⎠ γ /( γ −1) Then the velocity if gas discharging from the leak is sonic.1 to 1. pa = absolute downstream (atmospheric pressure (N/m2). 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.(4) Where GV = gas discharge rate (kg/s). R = gas constant (8314 J/kg-mol /oK).g. Thus for releases of most industrial gases to atmosphere. We define X.05. M = gas molecular weight (kg/kg-mol). Examples of Emission Source (Emergency Unplanned Releases) Gas discharge • Hole in equipment (pipe. T = storage pressure (N/m2) and temperature (oK). such that: X =( 2 (γ +1) /(γ −1) ) γ +1 . PS.71 to 2. 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..67.8).. γ = gas specific heat ratio (Cp/Cv. which give ‘r’ values of 1.(1) .9 bar absolute will result in sonic flow. A = hole area (m2).. In the above formula where ps = absolute upstream (storage pressure (N/m2).. Cd = discharge coefficient (~ 0.5 9 .SECTION II: ACCIDENT EFFECT ANALYSIS Table below shows the various accident scenarios and consequences feasible in an industrial scenario.

74.61) π (0.0 = 5. Cd = discharge coefficient (dimensionless).35 2 (γ +1) /(γ −1) ) γ +1 GV = (0.6 – 0. p = liquid storage pressure (N/m2 absolute). 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 = (0.81 m/s2).15 × 44 /(8314 × 298)}(0.3 barg At P = 10 barg.5 kg/s 3.(6) GLV = [AΛ/(ρg-1.Example: Calculate the discharge rate of propane through a 10-mm hole for conditions of 25oC and 4 barg (5 bara).8)(2) 490 = 1. the discharge will initially be liquid.1 m).0/1.. g = acceleration of gravity (9. Propane vapor pressure 25oC = 8.01) 2 / 4}(5 ×105 )[{1.0. 25oC with 2 m liquid head..8){π (0. ρl = liquid density (kg/m3). p = pvp) and equilibrium two-phase choked flow is established during release through a severed pipeline (i. Therefore use a gas discharge equation. TWO-PHASE FLOW If the liquid is stored at saturation (i. sharp edged orifices is 0.. the discharge must be as a pure gas.01) 2 4 (490) 2(10)(10 5 ) + 2(9.3 barg Since the total pressure is less than the vapor pressure of propane.e. nonflashing) liquids through a sharp-edged orifice/nozzle is given by: ⎛ 2( p − pa ) ⎞ GL = CdAρl ⎜ . Propane vapor pressure 25oC = 8.64. then the following equation is recommended: .e. Data: Propane heat capacity ratio = 1.15. Example: Calculate the discharge of propane from a tank through a 10-mm hole at 10 barg.35)]0. A= discharge hole area (m2).09kg / s 2. pa = downstream (ambient) pressure (N/m2 absolute).. Therefore use the liquid discharge model. Data: Propane density = 490 kg/m3. pipe length > 0. H = height of liquid above hole (m) The discharge coefficient for fully turbulent discharges from small.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 .. Here Ps /Pa = 5.e. LIQUID DISCHARGES Discharge of pure (i. the flow is sonic. Thus. which exceeds r = 1.5 = 0. X =( Thus X= 0.(5) + 2 gH ⎟ ρl ⎝ ⎠ Where GL = liquid mass emission rate (kg/s).

where Lp and D are pipe length and diameter.(6) should be multiplied by a factor.e boiling point at 5 bar = 130oC) Tb = atmospheric boiling point (69oC) Hvap = latent heat of vaporization at Tb = 3. respectively. Table 2: Variation of Factor F with Ratio Lp/D Lp/D F 1 0 0.(8) FV = CpΔT/Hvap Where Ts is process line/vessel temperature and Tb is normal boiling point temperature.Tb) oK . Frictional losses for saturated liquids For long pipe lengths the mass emission rate. the fluid flashes external to the hole. With this assumption the mass flow rate is given by Gm = ACo 2ρ f gc (P .. stored at temperature above the normal boiling point). then a more complicated numerical model is necessary to calculate the emission rate. Suggested values for F are given in Table 2.. in Eq.P sat ) . Data Cp = average liquid heat capacity (range T to Tb) ~2400 J/kg/oK T = operating temperature (i. The result will only be valid for liquids stored at a pressure higher than the saturation vapor pressure. Hvap the heat of vapourization at normal pressure. If the fluid path length through the release is greater than 10 cm (through a pipe or thick-walled container).65 200 0.43 ⎝ 340000 ⎠ Flashing liquids escaping through holes and pipes require very special consideration since two-phase flow conditions may be present. Example: Leak of hexane from a pressurized pipeline at 5 bar.. If this condition is not met. that accounts for frictional losses. F. and the liquid does not have time to flash within the hole. nonequilibrium conditions exist.e.55 400 4. The equations describing incompressible fluid flow through holes apply. GLV. Several special cases need consideration.4 x 105 J/kg Hence FV = 2400 ⎜ ⎛ 130 − 69 ⎞ ⎟ = 0.. FRACTION FLASHED FROM LIQUID DISCHARGE For superheated liquids (i. A good approximation is to assume a choked pressure equal to the saturation vapor pressure of the flashing liquid.(9) 11 .(7) x < p(ρg-1.ρl-1)(TsCpl)/Λ2 Where x is the weight fraction of vapor after depressurizing to atmospheric pressure. of the liquid emission is "flashed" to vapor as the pressure is reduced to ambient.75 100 0. f. If the fluid path length of the release is very short (through a hole in a thin-walled container).85 50 0. equilibrium flashing conditions are achieved and the flow is choked.This equation applies only if the following condition is met: . a fraction. This fraction is approximated from the thermodynamic relationship ΔT = (T .

The saturation vapor pressure of liquid ammonia at this temperature is 0. GLV = ( ) 2 = 7.. ΔHv = 3.0945 m) 2 / 4 x 2(603 kg/m 3 ) [1(kg m/s 2 ) / N] (1. At these conditions. A 1-cm diameter hole develops in the tank. Equation 9 applies for the case of equilibrium flashing conditions. A is the area of the release.(10) v fg C pT Small droplets of liquid also form in a jet of flashing vapor. For this case the choked.85 x 10-5 m2 ΔH v A v fg gc 7.85 x 10 -5 m 2 = (3.34 x 105 J/kg.18 x 103 J/kg K Equation 10 applies to this case. P is the pressure within the tank. Gm = ACo 2ρ f gc (P .774 kg/s 12 . Example: Propylene is stored at 25oC in a tank at its saturation pressure. for propylene.61. psat = 1.0945 m forms in the tank. and Psat is the saturation vapor pressure of the flashing liquid at ambient temperature. For liquids stored at their saturation vapor pressure. Cp = 2. These aerosol droplets are readily entrained by the wind and transported away from the release site.Example Liquid ammonia is stored in a tank at 24oC and a pressure of 1. Solution.P sat ) = (0.34 x 105 J/kg) (1 N m/J) Cp T 0. vfg = 0.968 x 10 6 ) (N / m 2 ) Gm = 97. A leak of diameter 0. Equilibrium flashing conditions can be assumed.2 m = A= 4 4 Using Equation 54.15 x 106 Pa.14)(0.042 m 3 / kg x ( ( ) ) (2. Assume a discharge coefficient of 0.6 kg/s Where.968 x 106 Pa and its density is 603 kg/m3. two-phase mass flow rate is given by: ΔH v A g c GLV = . The area of the leak is πd 2 (3.042 m3/kg. Determine the mass flow rate through the leak.14 ) 1 x 10 .18 x 10 1. Estimate the mass flow rate through the hole.4 x 106 Pa. Equation 10 is used. ρf is the density of the liquid (mass/volume).0(kg m/s 2 ) / N 3 J/kg K ( 298 K) (1N m/J) ) GLV = 0.61) (3. Co is the discharge coefficient (unitless).4 x10 6 − 0. The assumption that the quantity of droplets formed is equal to the amount of material flashed is frequently made. P = Psat.

Extremely unstable conditions. given by the formula Kg = DmNsh/d .(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). and it is necessary to model the evaporation from a surface pool. D. 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. 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.. the pool temperature is within a few degrees of ambient and the liquid does not boil).8-15200] .e.. The dispersion phenomenon depends on whether the gas is lighter or heavier than air. F.(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. B. TABLE 3 Pasquill Stability Meteorological Conditionsa. SLOWLY EVAPORATING POOL In many cases the hazardous material does not evaporate before it hits the ground surface. moderately unstable conditions.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. E. Plumes refer to with the travel time (time for cloud to reach location of 13 . Once released.037(km/Dm)1/3[(ud/km)0.5. If the rate of evaporation is light to moderate (i. and the liquid is well mixed.. C.. given by the correlation NSh = 0. moderately conditions. slightly unstable conditions. they will be dispersed by atmospheric conditions. slightly conditions. neutral conditions. Ge = kgApvpM/R*Tp .(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). then an empirical formula for slowly evaporating pools can be applied.

z = distance from source.y.04x0.80 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) 0.05x0.06x 0.92 A 0.082x0.093x0.92 0.91 D 0.337x 0.057x0.90 C 0.71 0.92 C 0.75 B 0.53x0.067x0.195x 0.18x0.92 0. Use of such formulas allow for easier computerization of the method.82 F 0.09x 0. FORMULA FOR INSTANTANEOUS PUFF EMISSIONS: ⎡ M y2 −( x − ut ) 2 −( z − H ) 2 −( z + H ) 2 ⎤ C ( x.087x1.70 E 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. t ) = exp{ ]}⎥ − 2 }{[ exp + exp ⎢ 2 (2π )3/ 2 σ xσ yσ z ⎢ 2σ x 2σ y 2σ z2 2σ z2 ⎥ ⎣ ⎦ .10x0. function of distance downwind.89 F 0. z ..91 E 0. Also because of a lack of data.34x0. 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 ⎦ ⎣ ⎦ . y. y = crosswind. σz).112x0.88 0. The basis for the PasquillGifford model is Gaussian dispersion in both the horizontal and vertical axes.85 0.15x0.128x0. M = amount released instantaneously (kg).65 0.(14) Where x.10 0. z. y .interest) or sampling (or averaging) time (normally 10 min).95 0.73 0.02x 0. these differ slightly.10x 0.92 D 0.135x0.(15) Where. t = time elapsed after release (s) Puff emissions have different spreading characteristics from continuous plumes and different dispersion coefficients (σy. σy. σz = dispersion coefficients (m). H = height of source above ground level plus plume rise (m). it is often assumed σx = σy.63 14 . GV = vapour emission rate (kg/s).90 0.90 0. m (x = downwind. z = vertical) c = concentration (kg/m3) at location x.14x0.493x A 0.88 B 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.60x0.

4) 2 ⎦ G RTa (0.3 = + exp exp exp ⎢ ⎥⎢ ⎥ 2π (9. 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. The release occurs at 2 m.5)(5. for fires the consequences of concern are thermal radiation effects.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)0.90 = 9. When explosions arise from a combustion reaction usually the thermal radiation effects are ignored because the shock wave effects will predominate.Example on Plume Discharge: Calculate the concentration of chlorine from a source of 0. An explosion can be thought of as a rapid equilibrium of a high-pressure gas with the environment. 10 m crosswind.4) 2 2(5. Gas constant. pressure p = 1 atm abs.3 m/s Dispersion coefficients for D stability evaluated at x = 120 m (using table above) σy = 0.128x0. Mo = 71. 5 m/s wind (at 10 m height). Ta = 20oC (293oK).e. assume that the plume is at near ambient temperature (Ta). R = 0. thus dispersion will rapidly ensure that the dense gas behaviour zone is negligible and a Gaussian model is adequate. within buildings or vessels) or an unconfined state (i. the plume is constrained by ground level. Then. Weather conditions correspond to D stability.25 = 3. Stability class = D.3 kg/s located 2 m above ground level at a place 120 m downwind..093x0. and 2 m height. The consequences of concern for explosions in general are shock wave overpressure effects and projectile effects.e.4)(3.5) 2 ⎦ ⎣ 2(5. This equilibrium must be rapid enough that the energy contained in the high-pressure gas is dissipated as a shock wave. unconfined vapor cloud explosions or UVCE). so the mean height for wind estimation is selected as 2 m.72 x 10-4 kg/m3 To convert this into ppm (vol).4 m Concentration in kg/m3 can be found from Equation (14): C= = 2.85 = 5.082)(293) x 106 = (2. Chlorine molecular weight.72 x 10-4) x 106 = 92 ppm PM o (1)(71) 2. Data: Assume ground roughness is equivalent to urban conditions. σz = 0. 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.. 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. Ambient temperature. These latter reactions can occur both in a confined state (i.5 m. The following accident scenarios are considered: • Unconfined Vapor Cloud Explosions and Flash Fires • BLEVE and Fireball • Pool Fire and Jet Fires 15 .3) ⎣ 2(9. The leak rate is small.

These estimates range from 1 ton to 15 tons. Ec = lower heat of combustion of flammable gas (kJ/kg or Btu/lb). η = empirical explosion yield (or efficiency) (ranges from 0. Scaled overpressure as a function of scaled distance 16 . and positive phase durations of 20-100 ms. The main consequence in a UVCE is the shock wave that results while the main consequence in a flash fire is the thermal radiation. a vapor cloud forms and disperses. A model of UVCEs is the TNT model. M = mass of flammable material released. Process structures contribute to partial confinement and turbulence. Two important mechanisms for flame acceleration are thermal expansion and turbulence. thus if many pieces of process equipment and many structures are present. typically 1 bar (15 psi) or less. It is based on the assumption of equivalence between the flammable material and TNT. 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.01 to 0. • Peak overpressures of UVCEs are much less than with detonations.(16) E cTNT where W = equivalent mass of TNT (kg or lb). factored by an explosion yield term: ηME c W= . EcTNT = heat of combustion of TNT (44374765 kJ/kg or 1943-2049 Btu/lb. it is likely that a flash fire will make the transition a UVCE. a UVCE or flash fire will occur. The TNT model is easy to use and has been applied for many CPQRAs.. If this cloud is ignited before the cloud is diluted below its LFL.Unconfined Vapor Cloud Explosions and Flash Fires When a large amount of a volatile flammable material is rapidly dispersed to the atmosphere. • The presence of some confinement/obstacles may be necessary for transition to UVCE. Figure 1.10). • Materials with higher fundamental burning velocities can produce easier transition to UVCE for a given release quantity.

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

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

heat of combustion = 43.35. Geometric View Factor: The thermal radiation received at a target location is determined by the geometric view factor (ignoring atmospheric absorption).35 x 2. not to the flux per unit area.66 The received thermal flux at 100 m is then calculated using Equation (27) Qx = τQRFp = 0. m2 Q = 0.09 = 0. Surface Emitted Power: LPG and LNG fires radiate up to 250 kW/m2. an equivalent diameter may be used. more rigorous formulas or tables are used.98 x 106 Kw x 8.02(Pwx)-0. Fp = point source view factor (m-2) 19 .(27) 2 Where Qx = thermal radiation received at distance x (kW/m ). but smoke obscuration often reduces this to 20-60 kW/m2.2 kW/m2 leakage rate.02(2320x100)-0.09 = 2. 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. QR = 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.700 kJ/kg. kJ/kg. as this radiant fraction is high for smoky pool fires) then the radiant heat. τ = atmospheric transmissivity (dimensionless). At closer distances.0 x 106 = 5. Weather conditions are no wind. FP = 1 1 = = 8. QR can be estimated. 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. Flame Height: Many observations of pool fires show that there is an approximate ratio of flame height to diameter. The radiation fraction of total combustion power is often quoted in the range 0.15-0. View factors are discussed in texts on thermal radiation. The point source view factor provides a reasonable estimate of received flux at distance far from the flame... x = distance from point source to target (m)./5 x 25)2 m2 = 2.13 kg/m2s x 43. Circular pools are normally assumed. Data: burning rate = 013 kg/m2s. kg/m2s.700 kJ/kg x π (0. where dikes lead to square or rectangular shapes. 20oC and 50% relative humidity. QR = total heat radiated (kW).35 (conservative.0 x 106 m-2 2 2 4πx 4π 100 Using Equation (23) for a distance of 100 m: τ = 2. This must be applied to the total heat output. Upper values for other hydrocarbon pool fires lie in the range 110-170 kW/m2. Ec = heat of combustion. 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: .8 x 106 kW = 9.(26) Fp = 1/ 4π x 2 -2 Where Fp = point source view factor (m ).8 x 106 kW Assume radiant fraction for hydrocarbon fires = 0. Typical values of H/D are in the range 2-3.66 x 0. Received Thermal Flux: The received thermal flux (on a target) from a pool fire is given by Qx = τQRFp .8 x 106 kJ/s = 2. A = pool area.8 x 105 kW.

97 20 Table 6: The Transformation from Percentages to Probits 0 1 2 3 4 5 6 7 8 -2.9 t0.92 3. Table 7 shows a variety of probit equations for a number of different types of exposures. overpressure due to an explosion or radiation intensity due to a fire).72 3.1 m0.48 4.29 4. Standard curve fitting techniques are used to determine the best fit straight line.12 3. The dimensions of the torch flame which is assumed to be conical. but subject to 1< m< 3000 kg/s).47 = 54 m Thus.50 = side-on hazard range to 50% lethality (m.. are given by (for LPG): .25 3. Example: Determine the 50% lethality range for a pressurized release of LPG @ 25 kg/s lasting for 100s.12 4. For single exposures.69 4.01 4.87 3.45 4.77 4.36 3. This relationship is tabulated in Table 6.33 4.(29) .16 4.75 4. ESTIMATION OF EFFECTS OF ACCIDENTS: PROBIT ANALYSIS Many methods exist for representing the response-dose curve.96 4.95 .85 4.05 4..67 4.50 4.39 4.47 = 1.5 W = 0.(28) L = 9. V. but subject to r>W). the side-on hazard zone for 50% lenthality is 54 m from the jet flame centerline.23 4.92 4. W = jet flame conical half-width at flame tip (m). but several reviews have been published.25L .45 3.59 3. From Equations (28)-(30) the jet flame dimensions are determined: L = 9.1 m0. the probit (probit = probability unit) method is particularly suited.50 = 1..( 32) 9 3. 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.90 4.47 where L = length of torch flame (m). while response implies the human/property damage caused by the accident.25L = 11 m (half width) rs.9 t0.08 4.Jet Fire Models: Jet fire modeling is not as well developed as for pool fires. M = LPG release rate (kg/sec.95 3.5 = 91 x 250.80 4. The probit variable Y is computed from the following equation: Probit = Y = k1 + k2 ln V % 0 10 20 30 40 .67 2..64 4.9x1000.82 3.56 4. Here dose refers to the intensity of accident outcome (air-borne concentration of a toxic material. but subject to 10<t<300s)The end-on hazard zone is 85% of the side-on hazard zone.87 4.72 4.66 4.(31) P= exp ⎜ − ⎟du ∫ ⎝ 2⎠ 2π −∞ Equation A provides a relationship between the probability P and the probit variable Y.(30) Rs..19 4.53 4.59 4.26 4.4 x 250.36 4.4 m0.52 3. rs.82 4.42 4.61 4. The causative factor represents the dose.77 3.5 = 45 m W = 0. t = exposure time (s.4 m0. The probit variable Y is related to the probability P (of a specified level of response) by: Y −5 ⎛ u2 ⎞ 1 .50 = 1.

992 (or 99.5%).71 6.25 5. 21 .28 5.18 7.44 5.31 5.91 po Eardrum ruptures -15.99 6.58 5.64 5.36 5.33 5.46 5.33 5. Table 7: Probit correlations for exposures.00 5.88 6.29 + 0.67.52 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 5.41 0. For a probability of 0.75 5.47 5. the probit is 5.28 0. Ychlorine = – 8. 8.79 o 2 p = peak overpressure (N/m ) Toxic release: Chlorine deaths -8.48 (or 48%) 6.3 7.9 8.74 6.64 0.10 5.41 5.58 4.2 7. For a probability of 0. For a probability of 0.6 1.1 2.36 the probability is 0.93 o p Structural damage -23. the causative variable V is representative of the magnitude of the exposure.8 (or 80%).1 6.0 7.39 5.23 7. Ie= effective radiation intensity received by target (W/m2) Explosion: Deaths from lung hemorrhage po -77. the probability is 0.61 5.2%) 7.8 7.9 2.41 5.05 0.58 5.995 (or 99.36 the probability is 0.20 5.09 Examples: 1.5 7.03 5.4 7.08 6.6 7.84 6. the probit is 3.67 6.Using table 3.55 0. For a probit of 3. For a probit less than 2. For a probit more than 8.95 the probability is 0.8 2.04 6.15 5.18 5.01 .05 5.81 6.13 5. Type of injury or damage Causative Probit variable Parameters V k1 k2 Fire: Burn deaths from fire -14.92 po Glass breakage -18.75 0.92 ln (C2t) = – 8.7 7.65 5.05 (or 5%) 5.34 0. For a probit of 7.09.13 6.92 ln (602 x 60) = 5.92 6.50 5.33 0.29 + 0. the probability of fatality is 50%.08 5.1 (or 10%) .23 5.84 3.48 0.77 6.95 6.88 5.29 0.55 5.56 teIe4/3/104 te= effective time of exposure (s). For a probit of 4.88 0.92 C2T C= concentration (ppm).72 2. the probability is 100%.37 5. the probit is 7.50 60 70 80 90 % 99 5.1 7.51 5.

The probit method has found less use for thermal injury than it has for toxic effects. 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.1 Threshold value below which escape should always be possible.91 ln 34455 = – 4.1 + 6.7) x 101300 N/m2 = 34455 N/m2 Hence Y = – 77.1 + 6. complete demolition of houses Relatively high blast overpressures (>15 psig) are necessary to produce fatality (primarily due to lung hemorrhage). 5. based on . Extreme pain within 20 seconds and movement to shelter is instinctive. t = duration of exposure (sec).91 ln (103365) = 2.56 ln tI 4/ 3 /10000 Where Pr = probit. Limiting flux for secondary fires.5 psi) 90% glass breakage No fatality and very low probability of injury 70 mbar (1 psi) • Internal partitions & joinery damaged.(33) nuclear explosion data.68 The probability of fatality is ~ 1%. 15psi overpressure is the approximate threshold for fatality.1 + 6. A probit model to estimate injury levels for a given thermal dose from pool and flash fires.91 ln p0 Now p0 = 5 psi = (5/14. Thus.. but can be repaired • Probability of injury is 10%. leading to fatality unless rescue is effected quickly.Table 9 Thermal Radiation Impact Criteria Criterion Level (kW/m2) 40 20 12.9 + 2. the chance is negligible) If overpressure is 15 psi (1 atm): Y = – 77. is: Yburn deaths = – 14. 22 . Example: What is chance of death from lung hemorrhage for an exposure to 5 psi blast pressure? From Table 7 Yfatality from hemorrhage = – 77. Incapacitation.5 Likely Effects at Criterion Level Immediate fatality. I = thermal radiation intensity (W/m2) Table 8 Explosion Impact Criteria Explosion Overpressure Effect • • 35 m bar (0.9 (From table 6. also.

9 + 2. may be inappropriate for such incidents. The overall probability of a failure in a process is dependent on the nature of this interaction.Example 1. Using the probit method. 23 .e-λt The failure density function f(t) is defined as: f(t) = dP(t) = λ e−λ t dt ∞ ...0 (Table 4).(2) P(t) = 1 . P. R is the reliability. This is called the average failure rate and is represented by λ with units of faults/time.00 ⎣ ⎦ Hence using table 6 the chance of fatality is ~ 2 % 2. λ. Equation (33) can be rearranged to solve for the thermal radiation intensity I: For t = 10 s..(3) The area under the plot of complete failure density function is unity. Between these two periods. 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 . 000) 4 / 3 /10000 ⎤ = 3. I = 11 kW/m2 This example demonstrates the importance of duration of exposure. 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. The probability the component will not fail during the time interval (0. A fixed criterion. I = ⎡104 e[(Pr + 14. The complement of the reliability is called the failure probability (or sometimes the unreliability). . Yburn deaths = –14. on the average.e. the failure rate is reasonably constant and Equation 2 through 4 are valid.56] / t ⎤ ⎣ ⎦ 2 3/ 4 .(1) R(t) = e-λt where. Data is collected on the failure rate of a particular hardware component.(4) Equations 1through 5 are only valid for a constant failure rate. What is the chance of human fatality for 20s exposure to 20kW/m2? Using Eq 33 (or table 7). suitable for prolonged exposures. With adequate data it can be shown that. Many components exhibit a typical "bathtub" failure rates.56 ln ⎡ 20(20. when t the reliability goes to 0.56 ln tI 4 / 3 /10000 = – 14.9 + 2. i. For t = 100 s. ∫ f(t)dt = 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). Determine the thermal flux necessary to cause 50% fatalities for 10 and 100 seconds of exposure.9) / 2. I = 61 kW/m . For 50% fatality.R(t) = 1 . the component fails after a certain period of time. Pr = 5. t) is given by: . Equation 1 assumes a constant failure rate. especially for short duration incidents such as BLEVEs (on the order of 10-20s). and is given by .

(7) ..70 Pressure gauge 1. 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. they are connected in a "Series" structure within a system. In such a case the system unreliability is: Psys = ∏P i =1 n i .13 Alarm Indicator lamp 0.022 Pressure switch 0. materials of construction. These are average values determined at a typical chemical process facility. or top event.(8) Psys = 1. The approach starts with a well-defined accident. in that.. These values depend on manufacturing practices employed by manufacturer.60 Hand valve 0. In some cases. is: Rsys = ∏R i =1 n i =1 n i .52 Thermometer 0. Events in fault 24 . Process components interact in two different ways.R ) i i =1 n .29 Control valve 0.044 Strip chart recorder 0.027 Valve positioner 0. a process failure requires the simultaneous failure of a number of components operating in a "parallel" mode. In such cases the overall process failure probability is computed from the individual component failure probabilities.41 Pressure relief valve 0.Pi ) Failure rate data for a number of typical process components are provided in Table 1. Process components also interact in series. and works backwards towards the various scenarios or events that can cause the accident.22 Thermocouple 0.. the physico-chemical environment in which the component functions etc. For series components the overall system process reliability.42 Stepper motor 0. Rsys = 1 - ∏ (1 .(5) where n is the total number of components and Pi is the failure probability of each.Interaction between Process Units Accidents in chemical plants are usually the result of a complicated interaction between a number of process components. Rsys.∏ (1 . design of the component.14 Solenoid valve 0.044 Level measurement meter (liquids) 1..(6) Where Ri is the reliability of an individual process component.

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

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

the horizontal line is continued through the safety function without branching. 27 . 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.Exothermic Reactor System If in a certain situation a safety function does not apply or is not relevant.

Event Tree for the Exothermic Reactor System 28 .

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

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

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

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. Angle = 22. Angle = 22. For drawing this transect the necessary numbers are shown in tables 2 and 3. of fatality = 1. of fatality = 1. Figure 6 is the individual risk profile in the northeast direction.1 x 10-5 IR = ∑ IRi = 32 . of fatality = 0 Prob. of fatality = 1. 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.50 Prob. For the example problem.Circle Diameter = 200m Prob.0 Prob.0 Circle Diameter = 100m Prob.i IRi (per year) -6 I 10 1 10-6 IIB2 10-5 1 10-5 1.50 Prob.0 N E Prob. of fatality = 0 Incident Outcome Case IIB1 Incident Outcome Case IIB2 Fig 3. of fatality = 0 Incident Outcome Case I Incident Outcome Case IIA Triangle Height = 400m. of fatality = 0 Prob.

67 Prob. = 0.6/yr IIB – No Ignition Toxic Cloud Prob. Individual Risk Contour Map 33 . = 0. f = 10 – 6/yr Prob. = 0.33 II – Flammable Toxic Gas Release. f = 10 – 6/yr IIA – Ignition (Explosion) f = 10 – 6/yr IIB1 – Toxic Cloud to Southwest. 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. = 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.

1 x 105 IIB2 1. IIB1 2. IIA 1. Individual Risk Transect in the Northeast direction 34 . IIB2 1. IIB2 2. IIB.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. IIA.1 x 10-5 I.0 x 10-5 I.6 10 .1 x 10-5 I.1 x 10-5 A I.0 x 10-5 IIB1 1.0 x 10-5 C I. IIA 1.1 x 10-5 I 1.1 x 10-5 I.5 10 .4 Individual Risk per year 10 . IIA.1 x 10-5 > 400 200 – 400 100 – 200 0 – 100 10 . IIA. IIB2 2. IIB2 1. B1 1.0 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 1.7 100 200 300 400 500 Distance from the Plant in the Northeast (m) Figure 6.1 x 10-5 I.

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

IIB1. Societal Risk F-N Curve 36 .4 Frequency of N or more Fatalities .7 1 10 100 Number of Fatalities (N) Figure 8.6 10 .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 10-5 0 IIB1 1.0 x 10-6 >13 + None 0 10 .5 10 .0 x 10-6 13 IIA 1.0 x 10-5 6 -5 IIB2 1. IIB2 2. IIB1 1.x 10-5 13 + I 1. per year 10 .1 x 10-5 6+ I.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.

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

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 .

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

possible runaway –do- 5. possible accumulation of unreacted materials 1. increases 1. 2. 3. Interlock with feed line 2. 4. None 1. high temperature alarm to alert operator Check and monitor reliability of water service Place controller on critical instrumentation list See 1A. 1. Stirrer motor malfunction Power failure 2B More 1. 2. Loss of cooling. Stirrer motor controller fails. 1. alarm 1. Not possible here 1. 1 Low water supply temperature 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. 2.3. 2. None 1. builds. Monomer feed continues. –do–do–do- 3. No mixing. possible runaway 1. Cooling water service failure Controller fails and closes valve Air pressure fails. 1. Install high flow alarm and/or cooling water high temp. reactant conc. Control valve fails open Controller fails and opens valve 1. High water supply temperature 1. 4. resulting in high motor speed 1. 2. 2. possible runaway –do–do1. 2.2 See 1A. Cooling system capacity limited temp. 1B High 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. Sooner than Later than Low High No 1. None.1 Instruct operators and update procedures See 1A-4 See 1A. 3. 5. 5. Monomer feed valve must fail closed on power loss 40 . Partially plugged cooling line Partial water source failure Control valve fails to respond 1. 1. possible runaway on heating – do Diminished cooling.2 Place valve on critical instrumentation list 1. possible accumulation of unreacted materials 2. 1. 2. 3. Interlock between cooling flow and reactor feed 1. 2. 1C Low Reactor cools. None 1. Temperature rises. 1. 4. 1. controller handles 1. closing valve 3. See1A. 2. None 1.

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

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

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

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

Thus: F (Xm) = 0.5 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: Skewness ≡ E[( X − μ )3 ] = ∫ ( x − μ )3 f ( x)dx −∞ ∞ For a symmetric distribution: Skewness ≡ E[( X − μ )3 ] = 0 If.Median (Xm) = value of ‘X’ at which values of X above and below are equally probable. the values of X > μ are more widely dispersed than X < μ. Skewness ≡ E[( X − μ )3 ] > 0 . 45 .

where‘s’ is an auxiliary (deterministic) variable. where: GX ( s) ≡ E (e sX ) . Skewness ≡ E[( X − μ )3 ] < 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 ) . 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 .If. Thus.

The probability density function f(x) is given by: 47 . σ z = 1 The Normal Distribution Curve Lognormal Distribution: The lognormal distribution is used quite frequently in reliability and safety studies.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. 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 .

49 . 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).