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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.

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.

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

Layers of Protection (Fig. 2)


Community Emergency Response Plant Emergency Response Physical Protection (Dikes) Physical Protection (Relief Devices) Automatic Action SIS or ESD Critical Alarms, Operator Supervision, Manual Intervention Basic Controls, Process Alarms, 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. For example, the likelihood of 10 fatalities at a specific location (x, y) is a type of societal risk measure. The calculation of societal risk requires the same frequency and consequence information as individual risk. Additionally, societal risk estimation requires a definition of the population at risk around the facility. This definition can include the population (e.g. residential, industrial, school), the likelihood of people being present, or mitigation factors. The difference between individual and societal risk may be illustrated by the following example. An office building located near a chemical plant contains 400 people during office hours and 1 guard at other times. If the likelihood of an incident causing a fatality at the office building is constant throughout the day, each individual in that building is subject to a certain individual risk. 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. However, the societal risk is significantly higher during office hours, when 400 people are affected, than at other times when a single person is affected. 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. The form of presentation will vary depending on the goal of the CPQRA and the measure of risk selected. The presentation may be on a relative basis (e.g. comparison of risk reduction benefits from various remedial measures) or an absolute basis (e.g. comparison with a risk target). Risk presentation provides a simple quantitative risk description useful for decision making. The number of incidents evaluated in a QRA may be very large. Risk presentation reduces this large volume of information to a manageable form. The end result may be a
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single-number index, a table, a graph (e.g. F-N plot), and/or a risk map (e.g. individual risk contour plot). Individual risk representation Common form of presentation of Individual Risk is risk contour plots (Figure 3). Risk contours (isorisk lines) connect points of equal risk around the facility. Places of particular vulnerability (e.g. schools, hospitals, population concentrations) may be quickly identified. Societal risk representation Societal risk addresses the number of people who might be affected by hazardous incidents. The presentation of societal risk was originally developed for the nuclear industry. A common form of societal risk is known as an F-N (Frequency-Number) curve. An F-N curve is a plot of cumulative frequency versus consequences (expressed as number of fatalities). A logarithmic plot is usually used because the frequency and number of fatalities range over several orders of magnitude. 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. Figure 4 shows an F-N curve for a single liquefied flammable gas facility. Another form of societal risk presentation is a tabulation of the risk of different group sizes of people affected (e.g. 1-10, 11-100, 101-1000). Acceptable Risk One cannot eliminate risk entirely. Every chemical process has a certain amount of risk associated with it. Risks from a process plant environment are always greater than the normal day-to-day risks taken by individuals in their non-industrial environment. For a single chemical process in a plant comprised of several process, this risk may be too high since the risks due to multiple exposures are additive. At some point in the design stage someone needs to decide if the risks are "acceptable". 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. From an engineering perspective, 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. The approach to risk management followed today is based on the ALARP (as low as reasonably practicable) principle, which is a three tiered framework as illustrated in Fig. 5 below.

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 7.3 14.5 x 10-5 Construction 5 10 x 10-5 Sector
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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

4.8 4 3.7 1.2 1.2 0.6 0.05 0.05

9.6 x 10-5 8 x 10-5 7.4 x 10-5 2.4 x 10-5 2.3 x 10-5 1.2 x 10-5 0.1 x 10-5 0.1 x 10-5

FAR= number of fatalities in 108 working hours; i.e., in a group of 1000 people for a working lifetime.

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. 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)

SECTION II: ACCIDENT EFFECT ANALYSIS Table below shows the various accident scenarios and consequences feasible in an industrial scenario. Examples of Emission Source (Emergency Unplanned Releases) Gas discharge Hole in equipment (pipe, 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., 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. 1. GAS DISCHARGE /( 1) +1 We define a ratio r = 2

..(1) ..(2)

Ps +1 If > Pa crit 2

/( 1)

Then the velocity if gas discharging from the leak is sonic. In the above formula where ps = absolute upstream (storage pressure (N/m2); pa = absolute downstream (atmospheric pressure (N/m2); = gas specific heat ratio (Cp/Cv, dimensionless) Typical values of range from 1.1 to 1.67, which give r values of 1.71 to 2.05. Thus for releases of most industrial gases to atmosphere, upstream pressures over ~ 1.9 bar absolute will result in sonic flow. We define X, such that:

X =(

2 ( +1) /( 1) ) +1

..(3)

Gas mass flow rate through an orifice is given by: ..(4) Where GV = gas discharge rate (kg/s); Cd = discharge coefficient (~ 0.8); A = hole area (m2); M = gas molecular weight (kg/kg-mol); R = gas constant (8314 J/kg-mol /oK); PS, T = storage pressure (N/m2) and temperature (oK).

GV = Cd APS {( M / RT ) X }0.5

Example: Calculate the discharge rate of propane through a 10-mm hole for conditions of 25oC and 4 barg (5 bara). Data: Propane heat capacity ratio = 1.15; Propane vapor pressure 25oC = 8.3 barg Since the total pressure is less than the vapor pressure of propane, the discharge must be as a pure gas. Therefore use a gas discharge equation. Here Ps /Pa = 5.0/1.0 = 5.0, which exceeds r = 1.74. Thus, the flow is sonic.

X =(
Thus X= 0.35

2 ( +1) /( 1) ) +1

GV = (0.8){ (0.01) 2 / 4}(5 105 )[{1.15 44 /(8314 298)}(0.35)]0.5 = 0.09kg / s

2. LIQUID DISCHARGES Discharge of pure (i.e., nonflashing) liquids through a sharp-edged orifice/nozzle is given by:

2( p pa ) GL = CdAl ..(5) + 2 gH l Where GL = liquid mass emission rate (kg/s); Cd = discharge coefficient (dimensionless); A= discharge hole area (m2); l = liquid density (kg/m3); p = liquid storage pressure (N/m2 absolute); pa = downstream (ambient) pressure (N/m2 absolute); g = acceleration of gravity (9.81 m/s2); H = height of liquid above hole (m) The discharge coefficient for fully turbulent discharges from small, sharp edged orifices is 0.6 0.64.
Example: Calculate the discharge of propane from a tank through a 10-mm hole at 10 barg, 25oC with 2 m liquid head. Data: Propane density = 490 kg/m3; Propane vapor pressure 25oC = 8.3 barg At P = 10 barg, the discharge will initially be liquid. Therefore use the liquid discharge model; p = 10 barg = 11 x 105 N/m2 abs pa = 1 x 105 N/m2 abs GL = CdAl

1/ 2

2( p pa )

+ 2 gH = (0.61)

(0.01) 2
4

(490)

2(10)(10 5 ) + 2(9.8)(2) 490

= 1.5 kg/s

3. TWO-PHASE FLOW If the liquid is stored at saturation (i.e., p = pvp) and equilibrium two-phase choked flow is established during release through a severed pipeline (i.e., pipe length > 0.1 m), then the following equation is recommended: ..(6) GLV = [A/(g-1- l-1)](TsCpl)-1/2 where GLV is total two-phase emission mass rate (kg/s) is latent heat of vaporization (J/kg) is gas density at storage pressure (kg/m3) g Ts is the storage temperature (oK) Cpl is specific heat of liquid (K/kg/oK)
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This equation applies only if the following condition is met: ..(7) x < p(g-1- l-1)(TsCpl)/2 Where x is the weight fraction of vapor after depressurizing to atmospheric pressure. If this condition is not met, then a more complicated numerical model is necessary to calculate the emission rate.
Frictional losses for saturated liquids For long pipe lengths the mass emission rate, GLV, in Eq.(6) should be multiplied by a factor, F, that accounts for frictional losses. Suggested values for F are given in Table 2, where Lp and D are pipe length and diameter, respectively. Table 2: Variation of Factor F with Ratio Lp/D Lp/D F 1 0 0.85 50 0.75 100 0.65 200 0.55 400 4. FRACTION FLASHED FROM LIQUID DISCHARGE For superheated liquids (i.e., stored at temperature above the normal boiling point), a fraction, f, of the liquid emission is "flashed" to vapor as the pressure is reduced to ambient. This fraction is approximated from the thermodynamic relationship T = (T - Tb) oK ..(8) FV = CpT/Hvap Where Ts is process line/vessel temperature and Tb is normal boiling point temperature, Hvap the heat of vapourization at normal pressure.
Example: Leak of hexane from a pressurized pipeline at 5 bar. Data Cp = average liquid heat capacity (range T to Tb) ~2400 J/kg/oK T = operating temperature (i.e boiling point at 5 bar = 130oC) Tb = atmospheric boiling point (69oC) Hvap = latent heat of vaporization at Tb = 3.4 x 105 J/kg Hence FV = 2400

130 69 = 0.43 340000

Flashing liquids escaping through holes and pipes require very special consideration since two-phase flow conditions may be present. Several special cases need consideration. If the fluid path length of the release is very short (through a hole in a thin-walled container), nonequilibrium conditions exist, and the liquid does not have time to flash within the hole; the fluid flashes external to the hole. The equations describing incompressible fluid flow through holes apply. If the fluid path length through the release is greater than 10 cm (through a pipe or thick-walled container), equilibrium flashing conditions are achieved and the flow is choked. A good approximation is to assume a choked pressure equal to the saturation vapor pressure of the flashing liquid. The result will only be valid for liquids stored at a pressure higher than the saturation vapor pressure. With this assumption the mass flow rate is given by Gm = ACo 2 f gc (P - P sat ) ..(9)

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Example Liquid ammonia is stored in a tank at 24oC and a pressure of 1.4 x 106 Pa. A leak of diameter 0.0945 m forms in the tank. The saturation vapor pressure of liquid ammonia at this temperature is 0.968 x 106 Pa and its density is 603 kg/m3. Determine the mass flow rate through the leak. Equilibrium flashing conditions can be assumed. Solution. Equation 9 applies for the case of equilibrium flashing conditions. Assume a discharge coefficient of 0.61. Gm = ACo

2 f gc (P - P sat ) = (0.61) (3.14)(0.0945 m) 2 / 4

x 2(603 kg/m 3 ) [1(kg m/s 2 ) / N] (1.4 x10 6 0.968 x 10 6 ) (N / m 2 ) Gm = 97.6 kg/s

Where, A is the area of the release, Co is the discharge coefficient (unitless), f is the density of the liquid (mass/volume), P is the pressure within the tank, and Psat is the saturation vapor pressure of the flashing liquid at ambient temperature. For liquids stored at their saturation vapor pressure, P = Psat, Equation 10 is used. For this case the choked, two-phase mass flow rate is given by: H v A g c GLV = ..(10) v fg C pT Small droplets of liquid also form in a jet of flashing vapor. These aerosol droplets are readily entrained by the wind and transported away from the release site. The assumption that the quantity of droplets formed is equal to the amount of material flashed is frequently made.
Example: Propylene is stored at 25oC in a tank at its saturation pressure. A 1-cm diameter hole develops in the tank. Estimate the mass flow rate through the hole. At these conditions, for propylene, Hv = 3.34 x 105 J/kg; vfg = 0.042 m3/kg; psat = 1.15 x 106 Pa; Cp = 2.18 x 103 J/kg K Equation 10 applies to this case. The area of the leak is

d 2 (3.14 ) 1 x 10 - 2 m = A= 4 4
Using Equation 54, GLV =

= 7.85 x 10-5 m2

H v A v fg

gc 7.85 x 10 -5 m 2 = (3.34 x 105 J/kg) (1 N m/J) Cp T 0.042 m 3 / kg


x

( (

) )

(2.18 x 10

1.0(kg m/s 2 ) / N
3

J/kg K ( 298 K) (1N m/J)

GLV = 0.774 kg/s

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5. SLOWLY EVAPORATING POOL In many cases the hazardous material does not evaporate before it hits the ground surface, and it is necessary to model the evaporation from a surface pool. If the rate of evaporation is light to moderate (i.e., the pool temperature is within a few degrees of ambient and the liquid does not boil), and the liquid is well mixed, then an empirical formula for slowly evaporating pools can be applied. Ge = kgApvpM/R*Tp ..(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), given by the formula Kg = DmNsh/d ..(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, given by the correlation NSh = 0.037(km/Dm)1/3[(ud/km)0.8-15200] ..(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). Once released, they will be dispersed by atmospheric conditions. The dispersion phenomenon depends on whether the gas is lighter or heavier than air. 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. TABLE 3 Pasquill Stability Meteorological Conditionsa,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, Extremely unstable conditions; B, moderately unstable conditions; C, slightly unstable conditions; D, neutral conditions; E, slightly conditions; F, moderately conditions.

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. Plumes refer to with the travel time (time for cloud to reach location of
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interest) or sampling (or averaging) time (normally 10 min). The basis for the PasquillGifford model is Gaussian dispersion in both the horizontal and vertical axes.
FORMULA FOR CONTINUOUS PLUME DISPERSION: GV y2 ( z H ) 2 ( z + H ) 2 exp{ 2 } exp{ } + exp{ } C= 2 y z u 2 y 2 z2 2 z2

..(14)

Where x,y,z = distance from source, m (x = downwind, y = crosswind, z = vertical) c = concentration (kg/m3) at location x, y, z; GV = vapour emission rate (kg/s); H = height of source above ground level plus plume rise (m); y, z = dispersion coefficients (m), function of distance downwind, u = wind velocity (m/s) Dispersion coefficients y and z for diffusion of Gaussian plumes are available aa predictive formulas for these are also available; these differ slightly. Use of such formulas allow for easier computerization of the method.
FORMULA FOR INSTANTANEOUS PUFF EMISSIONS: M y2 ( x ut ) 2 ( z H ) 2 ( z + H ) 2 C ( x, y , z , t ) = exp{ ]} 2 }{[ exp + exp 2 (2 )3/ 2 x y z 2 x 2 y 2 z2 2 z2 .(15) Where, M = amount released instantaneously (kg); t = time elapsed after release (s) Puff emissions have different spreading characteristics from continuous plumes and different dispersion coefficients (y, z). Also because of a lack of data, it is often assumed x = y. Table 4 Equations for Pasquill Gifford Dispersion Coefficients for Plume Dispersion (x = distance downwind from source) Pasquill-Gifford Stability class z(m) y (m) or x (m) 0.88 0.493x A 0.087x1.10 0.88 B 0.337x 0.135x0.95 0.90 C 0.195x 0.112x0.91 D 0.128x0.90 0.093x0.85 0.91 E 0.09x 0.082x0.82 F 0.067x0.90 0.057x0.80 Table 5 Equations for Pasquill Gifford Dispersion Coefficients for Puff Dispersion (x = distance downwind from source) Pasquill-Gifford Stability class z(m) y (m) or x (m) 0.18x0.92 A 0.60x0.75 B 0.14x0.92 0.53x0.73 0.92 C 0.10x 0.34x0.71 0.92 D 0.06x 0.15x0.70 E 0.04x0.92 0.10x0.65 0.89 F 0.02x 0.05x0.63

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Example on Plume Discharge: Calculate the concentration of chlorine from a source of 0.3 kg/s located 2 m above ground level at a place 120 m downwind, 10 m crosswind, and 2 m height. Weather conditions correspond to D stability, 5 m/s wind (at 10 m height). The leak rate is small, thus dispersion will rapidly ensure that the dense gas behaviour zone is negligible and a Gaussian model is adequate. The release occurs at 2 m, the plume is constrained by ground level, so the mean height for wind estimation is selected as 2 m. Data: Assume ground roughness is equivalent to urban conditions; Stability class = D; Ambient temperature, Ta = 20oC (293oK); pressure p = 1 atm abs; Chlorine molecular weight, Mo = 71; Gas constant, R = 0.082 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)0.25 = 3.3 m/s Dispersion coefficients for D stability evaluated at x = 120 m (using table above) y = 0.128x0.90 = 9.5 m; z = 0.093x0.85 = 5.4 m Concentration in kg/m3 can be found from Equation (14): C=

= 2.72 x 10-4 kg/m3 To convert this into ppm (vol), assume that the plume is at near ambient temperature (Ta). Then, Cppm =C

y2 ( z H ) 2 ( z + H ) 2 exp 2 exp + exp 2 y z u 2 y 2 z2 2 z2 102 (2 1) 2 (2 + 1) 2 0.3 = + exp exp exp 2 (9.5)(5.4)(3.3) 2(9.5) 2 2(5.4) 2 2(5.4) 2

RTa (0.082)(293) x 106 = (2.72 x 10-4) x 106 = 92 ppm PM o (1)(71)

2. 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. An explosion can be thought of as a rapid equilibrium of a high-pressure gas with the environment. This equilibrium must be rapid enough that the energy contained in the high-pressure gas is dissipated as a shock wave. 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. These latter reactions can occur both in a confined state (i.e., within buildings or vessels) or an unconfined state (i.e., unconfined vapor cloud explosions or UVCE). The consequences of concern for explosions in general are shock wave overpressure effects and projectile effects; for fires the consequences of concern are thermal radiation effects. When explosions arise from a combustion reaction usually the thermal radiation effects are ignored because the shock wave effects will predominate. The following accident scenarios are considered: Unconfined Vapor Cloud Explosions and Flash Fires BLEVE and Fireball Pool Fire and Jet Fires

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Unconfined Vapor Cloud Explosions and Flash Fires When a large amount of a volatile flammable material is rapidly dispersed to the atmosphere, a vapor cloud forms and disperses. If this cloud is ignited before the cloud is diluted below its LFL, a UVCE or flash fire will occur. The main consequence in a UVCE is the shock wave that results while the main consequence in a flash fire is the thermal radiation. Two important mechanisms for flame acceleration are thermal expansion and turbulence. Process structures contribute to partial confinement and turbulence, thus if many pieces of process equipment and many structures are present, it is likely that a flash fire will make the transition a UVCE. 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. These estimates range from 1 ton to 15 tons. The presence of some confinement/obstacles may be necessary for transition to UVCE. Materials with higher fundamental burning velocities can produce easier transition to UVCE for a given release quantity. Peak overpressures of UVCEs are much less than with detonations, typically 1 bar (15 psi) or less, and positive phase durations of 20-100 ms. A model of UVCEs is the TNT model. The TNT model is easy to use and has been applied for many CPQRAs. It is based on the assumption of equivalence between the flammable material and TNT, factored by an explosion yield term: ME c W= ..(16) E cTNT where W = equivalent mass of TNT (kg or lb); M = mass of flammable material released; = empirical explosion yield (or efficiency) (ranges from 0.01 to 0.10); Ec = lower heat of combustion of flammable gas (kJ/kg or Btu/lb); EcTNT = heat of combustion of TNT (44374765 kJ/kg or 1943-2049 Btu/lb.

Figure 1. Scaled overpressure as a function of scaled distance

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Example Using the TNT equivalent model, calculate the distance to 5 psi overpressure (equivalent to heavy building damage) of an UVCE of 10 short tons of propane. Data: Mass = 10 tons; Lower heat of combustion of propane (Ec) = 46350 kJ/kg; Assume an explosion yield () = 0.05; Assume EcTNT = 4650 kJ/kg From Equation (16), W =

ME c
E cTNT

= 0.05 x 10,000 x

46350 4650
=

= 4530 kg From Figure above, the scaled distance (ZG) to 5 psi (Pso m/kg1/3. Converting scaled distance to real distance: RG = ZG W1/3 = 7 m/kg1/3 x (4530 kg)1/3 = 113 m

0.33 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. 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. 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, weakening the container and leading to sudden shell rupture. A pressure relief valve does not protect against this mode of the failure. It should be noted, however, that a BLEVE can occur due to any mechanism that results in the sudden failure of containment allowing a superheated liquid to flash, typically increasing its volume over 200 times. This is sufficient to generate a pressure wave and fragments. If the released liquid is flammable, a fireball may result. Useful formulas for BLEVE physical parameters are Peak fireball diameter (m) Dmax = 6.48 M0.325 ..(18) Fireball duration (s) tBLEVE = 0.825 M0.26 ..(19) Center height of fireball (m) HBLEVE = 0.75 Dmax ..(20) Initial ground level hemisphere diameter (m) Dinitial = 1.3 Dmax ..(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. The radiation received by a target (for the duration of the BLEVE incident) is given by QR = EF21 ..(22) where QR = radiation received by a black body target (kW/m2) = transmissivity (dimensionless); E = surface emitted flux (kW/m2) F21= view factor (dimensionless) The atmospheric transmissivity , is an important factor. Thermal radiation is absorbed and scattered by the atmosphere. This causes a reduction in radiation received at target locations. The correlation formula that accounts for humidity is: = 2.02(Pwx)-0.09 ..(23) where = atmospheric transmissivity (fraction energy transmitted: 0 to 1); Pw = water partial pressure (Pascals, N/m2); x = path length, distance from flame surface to target (m)
17

Thermal radiation is usually calculated using surface emitted flux, E, rather than the Stefan-Boltzmann equation, as the latter requires the flame temperature. Typical heat fluxes in BLEVEs (200-350 kW/m2) are much higher than in pool fires as the flame is not smoky. The surface heat flux is based on the radiative fraction of the total heat of combustion. This fraction is typically 0.25-0.4. Frad MH c ..(24) E= ( Dmax ) 2 t BLEVE where E = surface emitted flux (kW/m2); M = mass of LPG in BLEVE (kg); Hc = heat of combustion (kJ/kg); Dmax = peak fireball diameter (m); Frad = radiation fraction, typically 0.25-0.40; TBLEVE= fireball duration (s) As the effects of a BLEVE mainly relate to human injury, a geometric view factor for a sphere to a surface normal to the sphere (not the horizontal or vertical components) should be used. D2 ..(25) F21 = 2 4r where F21 = view factor between sphere and target surface; D = sphere diameter (m) r = distance from sphere center to target along the ground (m)

BLEVE Schematic
Dmax

HBLEVE
X

Target

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. They tend to be localized in effect and are mainly of concern in establishing the potential for domino effects and employee safety zones, rather than for community risk. Pool and jet fire models, unlike those for dispersion and UVCE, 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. Pool fire models have been applied to LNG spills as well as more common flammable materials. The most common application of jet fire models is the specification of exclusion zones around flares. Pool Fire Models Burning Rate: Large pool fires burn at a constant vertical rate, characteristic for the material. Typical values for hydrocarbons are in the range 0.05 kg/m2s (gasoline) to 0.12 (LPG). Pool Size: In most cases, pool size is fixed by the size of release and by local physical barriers (e.g., dikes, sloped drainage areas). For a continuous leak, on an infinite flat plane, the maximum diameter is reached when the product of burning rate and surface area equals the

18

Example: Determine the thermal flux received at a distance of 100 m from a pool fire contained in a 25-m-diameter tank dike. Weather conditions are no wind, 20oC and 50% relative humidity. Data: burning rate = 013 kg/m2s; heat of combustion = 43,700 kJ/kg; 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, kg/m2s; Ec = heat of combustion, kJ/kg; A = pool area, m2 Q = 0.13 kg/m2s x 43,700 kJ/kg x (0./5 x 25)2 m2 = 2.8 x 106 kJ/s = 2.8 x 106 kW Assume radiant fraction for hydrocarbon fires = 0.35 (conservative, as this radiant fraction is high for smoky pool fires) then the radiant heat, QR can be estimated. QR = 0.35 x 2.8 x 106 kW = 9.8 x 105 kW, FP =

1 1 = = 8.0 x 106 m-2 2 2 4x 4 100

Using Equation (23) for a distance of 100 m: = 2.02(Pwx)-0.09 = 2.02(2320x100)-0.09 = 0.66 The received thermal flux at 100 m is then calculated using Equation (27) Qx = QRFp = 0.66 x 0.98 x 106 Kw x 8.0 x 106 = 5.2 kW/m2

leakage rate. Circular pools are normally assumed; where dikes lead to square or rectangular shapes, an equivalent diameter may be used. Flame Height: Many observations of pool fires show that there is an approximate ratio of flame height to diameter. Typical values of H/D are in the range 2-3. Surface Emitted Power: LPG and LNG fires radiate up to 250 kW/m2. Upper values for other hydrocarbon pool fires lie in the range 110-170 kW/m2, but smoke obscuration often reduces this to 20-60 kW/m2. 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. The radiation fraction of total combustion power is often quoted in the range 0.15-0.35. Geometric View Factor: The thermal radiation received at a target location is determined by the geometric view factor (ignoring atmospheric absorption). View factors are discussed in texts on thermal radiation. 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: ..(26) Fp = 1/ 4 x 2 -2 Where Fp = point source view factor (m ); x = distance from point source to target (m). This must be applied to the total heat output, not to the flux per unit area. The point source view factor provides a reasonable estimate of received flux at distance far from the flame. At closer distances, more rigorous formulas or tables are used. Received Thermal Flux: The received thermal flux (on a target) from a pool fire is given by Qx = QRFp ..(27) 2 Where Qx = thermal radiation received at distance x (kW/m ); = atmospheric transmissivity (dimensionless); QR = total heat radiated (kW); Fp = point source view factor (m-2)

19

Jet Fire Models: Jet fire modeling is not as well developed as for pool fires, but several reviews have been published. The dimensions of the torch flame which is assumed to be conical, are given by (for LPG): ..(28) L = 9.1 m0.5 W = 0.25L ..(29) ..(30) Rs,50 = 1.9 t0.4 m0.47 where L = length of torch flame (m); W = jet flame conical half-width at flame tip (m); M = LPG release rate (kg/sec; but subject to 1< m< 3000 kg/s); rs,50 = side-on hazard range to 50% lethality (m; but subject to r>W); t = exposure time (s; but subject to 10<t<300s)The end-on hazard zone is 85% of the side-on hazard zone.
Example: Determine the 50% lethality range for a pressurized release of LPG @ 25 kg/s lasting for 100s. From Equations (28)-(30) the jet flame dimensions are determined: L = 9.1 m0.5 = 91 x 250.5 = 45 m W = 0.25L = 11 m (half width) rs,50 = 1.9 t0.4 m0.47 = 1.9x1000.4 x 250.47 = 54 m Thus, the side-on hazard zone for 50% lenthality is 54 m from the jet flame centerline.

ESTIMATION OF EFFECTS OF ACCIDENTS: PROBIT ANALYSIS Many methods exist for representing the response-dose curve. Here dose refers to the intensity of accident outcome (air-borne concentration of a toxic material, overpressure due to an explosion or radiation intensity due to a fire), while response implies the human/property damage caused by the accident. For single exposures, the probit (probit = probability unit) method is particularly suited. The probit variable Y is related to the probability P (of a specified level of response) by: Y 5 u2 1 ..(31) P= exp du 2 2 Equation A provides a relationship between the probability P and the probit variable Y. This relationship is tabulated in Table 6. 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. Standard curve fitting techniques are used to determine the best fit straight line. Table 7 shows a variety of probit equations for a number of different types of exposures. The causative factor represents the dose, V. The probit variable Y is computed from the following equation: Probit = Y = k1 + k2 ln V % 0 10 20 30 40

..( 32)
9 3.66 4.12 4.45 4.72 4.97
20

Table 6: The Transformation from Percentages to Probits 0 1 2 3 4 5 6 7 8 -2.67 2.95 3.12 3.25 3.36 3.45 3.52 3.59 3.72 3.77 3.82 3.87 3.92 3.96 4.01 4.05 4.08 4.16 4.19 4.23 4.26 4.29 4.33 4.36 4.39 4.42 4.48 4.50 4.53 4.56 4.59 4.61 4.64 4.67 4.69 4.75 4.77 4.80 4.82 4.85 4.87 4.90 4.92 4.95

50 60 70 80 90 % 99

5.00 5.25 5.52 5.84 6.28 0.0 7.33

5.03 5.28 5.55 5.88 6.34 0.1 7.37

5.05 5.31 5.58 5.92 6.41 0.2 7.41

5.08 5.33 5.61 5.95 6.48 0.3 7.46

5.10 5.36 5.64 5.99 6.55 0.4 7.51

5.13 5.39 5.67 6.04 6.64 0.5 7.58

5.15 5.41 5.71 6.08 6.75 0.6 7.65

5.18 5.44 5.74 6.13 6.88 0.7 7.75

5.20 5.47 5.77 6.18 7.05 0.8 7.88

5.23 5.50 5.81 6.23 7.33 0.9 8.09

Examples: 1. For a probability of 0.1 (or 10%) , the probit is 3.72 2. For a probability of 0.8 (or 80%), the probit is 5.84 3. For a probability of 0.995 (or 99.5%), the probit is 7.58 4. For a probit of 3.36 the probability is 0.05 (or 5%) 5. For a probit of 4.95 the probability is 0.48 (or 48%) 6. For a probit of 7.36 the probability is 0.992 (or 99.2%) 7. For a probit less than 2.67, the probability is 0. 8. For a probit more than 8.09, the probability is 100%.

Table 7: Probit correlations for exposures, the causative variable V is representative of the magnitude of the exposure. Type of injury or damage Causative Probit variable Parameters V k1 k2 Fire: Burn deaths from fire -14.9 2.56 teIe4/3/104 te= effective time of exposure (s); Ie= effective radiation intensity received by target (W/m2) Explosion: Deaths from lung hemorrhage po -77.1 6.91 po Eardrum ruptures -15.6 1.93 o p Structural damage -23.8 2.92 po Glass breakage -18.1 2.79 o 2 p = peak overpressure (N/m ) Toxic release: Chlorine deaths -8.29 0.92 C2T C= concentration (ppm); 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, Ychlorine = 8.29 + 0.92 ln (C2t) = 8.29 + 0.92 ln (602 x 60) = 5.01 .Using table 3, the probability of fatality is 50%.

21

Table 9 Thermal Radiation Impact Criteria Criterion Level (kW/m2) 40 20 12.5 Likely Effects at Criterion Level

Immediate fatality. Incapacitation, leading to fatality unless rescue is effected quickly. Extreme pain within 20 seconds and movement to shelter is instinctive. Limiting flux for secondary fires. 5.1 Threshold value below which escape should always be possible. The probit method has found less use for thermal injury than it has for toxic effects. A probit model to estimate injury levels for a given thermal dose from pool and flash fires, based on ..(33) nuclear explosion data, is: Yburn deaths = 14.9 + 2.56 ln tI 4/ 3 /10000 Where Pr = probit; t = duration of exposure (sec); I = thermal radiation intensity (W/m2)
Table 8 Explosion Impact Criteria
Explosion Overpressure Effect

35 m bar (0.5 psi)

90% glass breakage No fatality and very low probability of injury 70 mbar (1 psi) Internal partitions & joinery damaged, but can be repaired Probability of injury is 10%. 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; also, complete demolition of houses Relatively high blast overpressures (>15 psig) are necessary to produce fatality (primarily due to lung hemorrhage).
Example: What is chance of death from lung hemorrhage for an exposure to 5 psi blast pressure? From Table 7 Yfatality from hemorrhage = 77.1 + 6.91 ln p0 Now p0 = 5 psi = (5/14.7) x 101300 N/m2 = 34455 N/m2 Hence Y = 77.1 + 6.91 ln 34455 = 4.9 (From table 6, the chance is negligible) If overpressure is 15 psi (1 atm): Y = 77.1 + 6.91 ln (103365) = 2.68 The probability of fatality is ~ 1%. Thus, 15psi overpressure is the approximate threshold for fatality.

22

Example 1. What is the chance of human fatality for 20s exposure to 20kW/m2? Using Eq 33 (or table 7), Yburn deaths = 14.9 + 2.56 ln tI 4 / 3 /10000 = 14.9 + 2.56 ln 20(20, 000) 4 / 3 /10000 = 3.00 Hence using table 6 the chance of fatality is ~ 2 % 2. Determine the thermal flux necessary to cause 50% fatalities for 10 and 100 seconds of exposure. Using the probit method, Equation (33) can be rearranged to solve for the thermal radiation intensity I: For t = 10 s, I = 61 kW/m ; For t = 100 s, I = 11 kW/m2 This example demonstrates the importance of duration of exposure, especially for short duration incidents such as BLEVEs (on the order of 10-20s). A fixed criterion, suitable for prolonged exposures, may be inappropriate for such incidents. I = 104 e[(Pr + 14.9) / 2.56] / t
2
3/ 4

; For 50% fatality, Pr = 5.0 (Table 4).

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 overall probability of a failure in a process is dependent on the nature of this interaction. Data is collected on the failure rate of a particular hardware component. With adequate data it can be shown that, on the average, the component fails after a certain period of time. This is called the average failure rate and is represented by with units of faults/time. The probability the component will not fail during the time interval (0, t) is given by: ..(1) R(t) = e-t where, R is the reliability. Equation 1 assumes a constant failure rate; when t the reliability goes to 0. The complement of the reliability is called the failure probability (or sometimes the unreliability), P, and is given by . .(2) P(t) = 1 - R(t) = 1 - e-t The failure density function f(t) is defined as:

f(t) =

dP(t) = e t dt

..(3)

The area under the plot of complete failure density function is unity, i.e., f(t)dt = 1 .
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 = 0

..(4)

Equations 1through 5 are only valid for a constant failure rate, . Many components exhibit a typical "bathtub" failure rates. 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). Between these two periods, the failure rate is reasonably constant and Equation 2 through 4 are valid.
23

Interaction between Process Units Accidents in chemical plants are usually the result of a complicated interaction between a number of process components. In such cases the overall process failure probability is computed from the individual component failure probabilities. Process components interact in two different ways. In some cases, a process failure requires the simultaneous failure of a number of components operating in a "parallel" mode. In such a case the system unreliability is:

Psys =

P
i =1

..(5)

where n is the total number of components and Pi is the failure probability of each. Rsys = 1 -

(1 - R )
i i =1

..(6)

Where Ri is the reliability of an individual process component. Process components also interact in series, in that, they are connected in a "Series" structure within a system. For series components the overall system process reliability, Rsys, is: Rsys =

R
i =1 n i =1

..(7) ..(8)

Psys = 1- (1 - Pi )

Failure rate data for a number of typical process components are provided in Table 1. These are average values determined at a typical chemical process facility. These values depend on manufacturing practices employed by manufacturer, materials of construction, design of the component, the physico-chemical environment in which the component functions etc.
Table 1 Failure Rate Data for various selected process components Instrument Faults/year Controller 0.29 Control valve 0.60 Hand valve 0.13 Alarm Indicator lamp 0.044 Level measurement meter (liquids) 1.70 Pressure gauge 1.41 Pressure relief valve 0.022 Pressure switch 0.14 Solenoid valve 0.42 Stepper motor 0.044 Strip chart recorder 0.22 Thermocouple 0.52 Thermometer 0.027 Valve positioner 0.44 FAULT TREES Fault trees are a deductive method for identifying ways in which hazards can lead to accidents. The approach starts with a well-defined accident, or top event, and works backwards towards the various scenarios or events that can cause the accident. Events in fault
24

tree are not restricted to hardware failures. It can also include software failure, human error, and environmental abnormities. For reasonably complex chemical processes, 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. OR gate is used for describing events that need occur alone to result in output event. 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

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

26

Exothermic Reactor System

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

27

Event Tree for the Exothermic Reactor System

28

QRA: A CASE STUDY The chemical plant X considered is a very simple one, where most phenomena occur as simple step functions. In the company X the following apply: All hazards originate at a single point. Only two weather conditions occur. The atmospheric stability class and wind speed are always the same. Half of the time the wind blows from the northeast, and half of the time it blows from the southwest. There are people located around the site. The specific population distribution will be described later in the example, when the information is needed. Incident consequences are simple step functions. The probability of fatality from a hazardous incident at a particular location is either 0 or 1. These simple conditions, and the description of the impact zones of incidents as simple geometric areas, allow easy hand calculation of various risk measures, and is used primarily to illustrate the QRA methodology. 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. These models include:

1. Estimation of accident consequence: source and dispersion models 2. Estimation of effects of accident effects on human and property: probit Analysis 3. Estimation of Accident frequency: reliability, 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. Using industry-wide historical data, as well as HAZID techniques, the following realistic scenarios are identified for X: I. An explosion resulting from detonation of an unstable chemical. A release of a flammable, toxic gas resulting from failure of a vessel. II. Incident Outcomes The identified incidents may have one or more outcomes, depending on the sequence of events which follows the original incident. For example, a leak of volatile, flammable liquid from a pipe might catch fire immediately (jet fire), might form a flammable cloud which
29

could ignite and burn (flash fire) or explode (vapor cloud explosion). The material also might not ignite at all, resulting in a toxic vapor cloud. These are referred to as potential accident scenarios or as incident outcomes. Some incident outcomes are further subdivided into incident outcome cases, differentiated by the weather conditions and wind direction, if these conditions influence the potential damage resulting from the incident. Event tree logic may be used to identify the incident outcomes and outcome cases. Incident I, the explosion has only one possible outcome (the explosion), and the consequence and effects are unaffected by the weather. Therefore, for Incident I there is only one incident outcome and one incident outcome case; this is represented by an event tree with no branches (Fig 2).

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, the release of flammable, toxic gas, has several possible outcomes (jet fire, vapor cloud fire, vapor cloud explosion, toxic cloud) and its event tree is also shown in fig 2. (Note that for simplicity only two wind directions are assumed for the outcomes cases). Consequence and Impact Analysis Incident impact estimation requires two steps. 1. Estimation of a physical concentration of material or energy at each location starting from the point of origin of the incident: radiant heat from a fire, overpressure from an explosion, concentration of a toxic material in the atmosphere 2. Estimation of the effects (impact) that this physical concentration of material or energy has on people, the environment, or property for example, toxic material dose-response relationships (probit equations). 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 = 1.0); all persons beyond this distance are unaffected (probability of fatality = 0). Incident Outcome Case IIA (explosion) the explosion is centered at the center point of the facility; all persons within 100 meters of the explosion center are
30

killed (probability of fatality = 1.0); all persons beyond this distance are unaffected (probability of fatality = 0). Incident Outcome Cases IIBI, IIB2 (toxic gas clouds) all persons in a pie shaped segment of radius 400 meters downwind and 22.50 width are killed (probability of fatality = 1.0); all persons outside this area are unaffected (probability of fatality = 0). Figure 3 illustrates these impact zone.
Incident Frequency Analysis Reliability, fault and event tree methods are used for accident frequency estimation. We assume that the following values obtain for the 2 potential incidents on X: Incident I Frequency = 1 x 10-6 events per year Incident II Frequency = 3 x 10-6 events per year (for Incident II Ignition Probability = 0.33) We further assume that annually, the wind blows from the Northeast 50% of the time, and from the Southwest 50% of the time. The above considerations give the frequency estimates for the four incident outcome cases (shown in the event trees of Figure 4). Individual Risk Estimation Individual risk is defined as The risk to a person in the vicinity of a hazard. This includes the nature of the injury to the individual, the likelihood of the injury occurring, and the time period over which the injury might occur. In this example, the nature of the injury for both individual and societal risk calculations will be immediate fatality resulting from fire, explosion, or exposure to toxic vapors. Individual Risk Contours Individual risk at any point is given by:

IRx,y = where;

IR
i =1

x, y,I

..(1) ..(2)

IRx,y,I = fi pf,i

IRx,y = the total individual risk of fatality at geographical location x,y (probability of fatality per year) IRx,y,i = the individual risk of fatality at geographical location x,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, (per year) fi pf,i = probability that incident outcome case I will result in a fatality at location x, y Each incident outcome case has an equal impact (probability of fatality pf,i = 1) throughout its geographical impact zone. Therefore, within the impact zone for each incident outcome case, the individual risk from that incident outcome case IRx,y,i is equal to the frequency of that incident outcome case (Equation 2). Outside the impact zone, IRx,y,i is zero. 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. 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). For example, in the area labeled C in Figure 5, application of Equation 1 gives the results listed in Table 1.

Similar calculations for the other areas in Figure 5 give the results summarized in Table 2. Figure 5 is an individual risk contour plot for this example problem, with the individual risk values for each area listed in Table 2.
31

Circle Diameter = 200m Prob. of fatality = 1.0

Circle Diameter = 100m

Prob. of fatality = 0 Prob. of fatality = 1.0

Prob. of fatality = 0

Incident Outcome Case I

Incident Outcome Case IIA

Triangle Height = 400m; Angle = 22.50 Prob. of fatality = 1.0

Triangle Height = 400m; Angle = 22.50 Prob. of fatality = 1.0

N E
Prob. of fatality = 0 Prob. of fatality = 0

Incident Outcome Case IIB1

Incident Outcome Case IIB2

Fig 3. 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. For the example problem, Figure 6 is the individual risk profile in the northeast direction. For drawing this transect the necessary numbers are shown in tables 2 and 3.
Table 1 Individual Risk Calculation for Area C In Figure 5 Incident Outcome Case fi (per year) Pf,i IRi (per year) -6 I 10 1 10-6 IIB2 10-5 1 10-5 1.1 x 10-5 IR = IRi =

32

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. = 0.33 II Flammable Toxic Gas Release; f = 3x10 - 6/yr IIB No Ignition Toxic Cloud Prob. = 0.67 Prob. = 0.5 IIB2 Toxic Cloud to Northeast; f = 10 6/yr IIA Ignition (Explosion) f = 10 6/yr IIB1 Toxic Cloud to Southwest; f = 10 6/yr Prob. = 0.5

Figure 4. 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

Figure 5. Individual Risk Contour Map

33

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, IIB2 2.1 x 10-5 I, IIA, IIB1 2.1 x 10-5 I, IIB2 1.1 x 10-5 I, IIB, B1 1.1 x 105 IIB2 1.0 x 10-5 IIB1 1.0 x 10-5 I, IIA 1.1 x 10-5 I, IIA 1.1 x 10-5 I 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 1.0 x 10-5 C I, IIB2 1.1 x 10-5 A I, IIA, IIB2 2.1 x 10-5

> 400 200 400 100 200 0 100

10 - 4 Individual Risk per year

10 - 5

10 - 6

10 - 7

100

200

300

400

500

Distance from the Plant in the Northeast (m)

Figure 6. Individual Risk Transect in the Northeast direction

34

Figure 7 shows the location of people in the area surrounding the CP facility.
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. Population Distribution in and around CP Societal Risk Calculation Societal risk measures the risk to a group of people. Societal risk measures estimate both the potential size and likelihood of incidents with multiple adverse outcomes. In this example, the adverse outcome considered is immediate fatality resulting from fire, explosion, 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. F-N Curve A common measure of societal risk is the Frequency-Number (F-N) curve. 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, as determined by: Ni = Px , y Pf ,i ..(5)

x, y

where Ni is the number of fatalities resulting from Incident Outcome Case i. For the example, pf,i in Equation 5 equals 1. Because the impact zones for the example are simple, 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. Table 4 summarizes the estimated number of fatalities for the four incident outcome cases. The data in Table 4 must then be put into cumulative frequency form to plot the F-N ..(6) Curve: FN = Fi ; for all outcome cases i for which Ni N

where: FN = frequency of all incident outcome cases affecting N or more people, per year ; Fi = frequency of incident outcome case i, per year

Table 5 summarizes the cumulative frequency results. The data in Table 5 can be plotted to give the societal risk F-N Curve in Figure 8.
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Table 4 Estimated Numbers of Fatalities from Each Incident Outcome Case Incident Outcome Case Frequency Fi Estimated Number of Fatalities (per year) I 1.0 x 10-6 13 IIA 1.0 x 10-5 0 IIB1 1.0 x 10-5 6 -5 IIB2 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, IIB1, IIB2 2.1 x 10-5 6+ I, IIB1 1.x 10-5 13 + I 1.0 x 10-6 >13 + None 0

10 - 4 Frequency of N or more Fatalities , per year

10 - 5

10 - 6

10 - 7

10

100

Number of Fatalities (N)

Figure 8. Societal Risk F-N Curve

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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 plant is split into a number of parts. Each part is subjected to a number of questions based on a set of guidewords for the project. The purpose is to identify all possible deviations from the design conditions and to identify all the hazards associated with these deviations. The basic concept behind HAZOP studies is that processes work well when operating under design conditions, deviations from the process design conditions cause hazards and lead to operability problems. Where deviations result in hazards, actions are identified. This requires the design engineer to review and suggest solutions to either remove the hazard or reduce its risk to an acceptable level. These solutions are reviewed and accepted by the HAZOP team before implementation. The questions are formulated using a number of guide words to ensure a consistent and structured approach. The application of an accepted set of guide words ensures that every conceivable deviation is considered. The guide words are normally applied in conjunction with a series of process parameters to arrive at a meaningful deviation. The main process parameters with their commonly used guide words are as follows:
Main Process Parameters flow temperature, pressure, level composition, reaction, phase Commonly Used Guide Words

no, more, less, reverse, sneak (leak) higher, lower no, more, less, as well as, part of, other than

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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

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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. Control valve fails closed Plugged cooling coils 1. 2. Loss of cooling, possible runaway do-

Action required 1. 2. Select valve to fail open Install filter with maintenance procedure Install cooling water flow meter and low flow alarm Install

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3. 4. 5.

Cooling water service failure Controller fails and closes valve Air pressure fails, closing valve

3. 4. 5.

dododo-

3. 4.

1B

High

1. 2.

Control valve fails open Controller fails and opens valve 1. 2. 3. Partially plugged cooling line Partial water source failure Control valve fails to respond 1. 1. 1. 2. 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. 2. 1. 2. 3.

1C

Low

Reactor cools, reactant conc. builds, possible runaway on heating do Diminished cooling, possible runaway dodo1. Not possible here 1. 2. Loss of cooling, possible runaway do-

5. 1. 2. 1. 2. 3.

high temperature alarm to alert operator Check and monitor reliability of water service Place controller on critical instrumentation list See 1A.1 Instruct operators and update procedures See 1A-4 See 1A.2 See 1A.2 Place valve on critical instrumentation list 1. None 1. 2. See1A.2 Install check calve

1D 1E 1F

As well as Part of Reverse

1G 1H 1I 1J 1K 2A Stirrer Temperature Agitation

Other than, Sooner than Later than Low High No

1. 1. 1.

1 Low water supply temperature 1. High water supply temperature 1. 2. Stirrer motor malfunction Power failure

2B

More

1. Stirrer motor controller fails, resulting in high motor speed

1. None 1. Temperature rises, possible runaway 1. None; controller handles 1. Cooling system capacity limited temp. increases 1. No mixing, possible accumulation of unreacted materials 2. Monomer feed continues, possible accumulation of unreacted materials 1. None

1. Interlock between cooling flow and reactor feed 1. None 1. Install high flow alarm and/or cooling water high temp. alarm 1. Interlock with feed line 2. Monomer feed valve must fail closed on power loss

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PROBABILITY THEORY IN CHEMICAL RISK ASSESSMENT

The probability concept is the basis for a risk analysis or reliability analysis. One must be familiar with this concept to be able to determine the value of the input parameters and to understand the results of a risk or reliability analysis. A, 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:

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It follows that:

For independent events:

If events are dependent:

Bayesian Estimation

We know that in general:

For any arbitrary event Ai

Or:

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Lets consider that one has a set events Ai which are exhaustive and mutually exclusive. Exhaustive implies that every conceivable outcome is included in the prior distribution.

A3 A1 AB A2

Considering Ai as class i, the following conditions hold:

Using the previous relations:

The last expression is Bayes theorem. The equation is valid in general for any number of events A1, A2,, An. It is important to understand the meaning of the various terms in the Bayes expression: B: Collected plant-specific data. P(Ai) : Probability of Ai, prior to learning fact B.(i.e., Available generic data) P(B|Ai) : The probability of the observation, given that A, is true. (i.e., Updated failure data) P(Ai|B) : Probability of Ai after learning fact B.

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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.

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)

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Median (Xm) = value of X at which values of X above and below are equally

probable. Thus: F (Xm) = 0.5

Mean (or Expectation):

E( X ) = =

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 ) = 2 = ( x ) 2 f ( x)dx

Standard Deviation:

( X ) = Var ( X )
Coefficient of Variation:

COV = ( X ) = ( X ) / ( X ) The COV gives the relative spread of X around its mean value.
Skewness:
Skewness E[( X )3 ] = ( x )3 f ( x)dx

For a symmetric distribution: Skewness E[( X )3 ] = 0 If, Skewness E[( X )3 ] > 0 , the values of X > are more widely dispersed than X < .
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If, Skewness E[( X )3 ] < 0 , the values of X < are more widely dispersed than X > .
Skewness Coefficient:

E[( X )3 ]

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 ) , where: GX ( s) E (e sX ) , wheres is an auxiliary (deterministic) variable. Thus, 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) = e x F ( x) = 1 e x
Normal Distribution:

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Standard Normal Distribution:

It follows that:

z = 0, z = 1

The Normal Distribution Curve Lognormal Distribution:

The lognormal distribution is used quite frequently in reliability and safety studies. The relationship to normal distribution is as follows: if the stochastic variable ln(x) has a normal distribution, x has a lognormal distribution. The probability density function f(x) is given by:

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The Lognormal Distribution Curve Weibull distribution:

= shape parameter = lowest value life parameter = characteristic life Typical shapes of f(x) is shown below with = 0

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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). The Poisson distribution is a discrete probability distribution and not a probability density distribution.

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