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WORLD BANK TECHNICAL PAPER NUMBER 55 WTP55 Techniques for Assessing Industrial Hazards A Manual Technica, Ltd. .... v < D- ., o r 8 ; z|jL -_ _ ~~~~~~~~~~~~~~., -- '_>,, -A.- yt' sj,~~ L r, XA,, .'"~ *' / I~~~~~~ M: =X ~~~~~~~~~~~~~~- ~ 2~~~~~I:L -OF Public Disclosure Authorized Public Disclosure Authorized Public Disclosure Authorized Public Disclosure Authorized

Manual of Industrial Hazards Assessment

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Techniques for Assessing Industrial HazardsA Manual

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; 170 0 C in the presence of traces of catalyst. Means of Control - Use of thin film evaporation. Steam at 150 0 C, water dousing system, relief to blowdown drum Temp. Alarms and interlocks.-

Small quantities only in

process. 2. Reaction stepnitration of Chemical B. Highly exothermic reaction with catalyst. - Continuous reaction system with small quantities of reactions in large quantity of liquid catalyst recycle.- Reactants metered by


Reaction step-

nitration of Chemical C.

Highly exothermic reaction with H 2 SO 4

as catalyst.

dosing pump system with special safeguards. Reaction takes place in pump after static mixer. Temp. alarms and interlocks to prevent runaway reactions.-

Small quantities of

reactants. 4. Reboilers of distillation columns in purification stages. Runaway polymerisation reaction. - Small quantity of material with temperature control. Safe discharge of reboiler contents to an enclosed area away from other process equipment and personnel via a rupture disc relief system andvent angled at 450 to

horizontal < 100 kg products. Summary of Reactive Hazards 161


Reboilers of distillation columns in purification stages.

Runaway polymerisation reaction.

- Small quantity of material with temperature control. Safe discharge of reboiler contents to an enclosed area away from other process equipment and personnel via a rupture disc relief system andvent angled at 450 to

horizontal < 100 kg products.


Reaction step -

Highly exothemnic in


Over designed extemal

Hydrolysis of Chemical D at 160 0 C and 4 atmos. All reactants are added at start of batch and heatedto operating

10 m3 reactors. Scale up from 100 litre pilot plant and operating 3 experience on 3 m reactor with similar reactants.

coil cooling system for heat of reaction of 41 kcal/mol cf. actual value of 14 kcal/mol.-

Manual blow-down on reactor.Semi-automatic blow-


temperature of 1500 C.

down system from control room.- Computer control to

minimise human error.- Relief valve system to

blow-down. 6. Two step reaction process. First step involving catalytic reduction of Chemical E to Chemical F is the hazardous step. If insufficient active catalyst (i.e., due to poisoning or inadequate addition), and too low a reaction temperature, a build up of an intermediate product occurs. This intermediate can cause a runaway reaction if the temperature is raised too quickly. - Extended batch reaction cycle from 1/2 hour to 3 hours. - Keep reaction temperature > 80 0 C. - Control flow of H 2 . - Shut off flow of H 2 if temperature < 800C.


Summary of Reactive Hazards


Catalytical reduction of Chemical G in a continuous reactor at 60 atmosphere's pressure.

Similar reaction hazard as - Fully computer Unit 6, if the intermediate controlled. forms due to insufficient active catalyst and too low - Hydrogen addition temperature. This is the regulated according to first time this reactor heat balance calculations. system has been used to produce Chemical H. - Auto shut-off of H 2 if Has been used for similar heat balance shows reactions and an extensive generation of intercomputer control/safety mediate. system has been developed. - Initially there will be no recycle of catalyst but may recycle as gain experience. - Reactor blow-down system installed. - Safety interlocks. - Significant volumne of chemicals present.

Summarv of Reactive Hazards


APPENDIX CSummary of Potential Sources of Ignition REDUCTION OF IGNITION RISKIndustrial plants contain a great number of possible ignition sources.It is common practice to reduce as far as practical possible ignition sources in areas where there is a risk of flammable releases. This is achieved by enforcing regulations that: a) restrict activity in the area (using a "permit to work system") b) only allow suitable equipment in the area c) restrict access to the area (by fencing off the area)

LIST OF IGNITION SOURCESLees ( 1980 ) lists likely ignition sources. The list is given here with suggestions on how ignition sources should be controlled within a restricted area. Ignition Source 1. Bumer flames. 2. 3. Buming operations. Hot soot. No-smoking in restricted area. Method of Control Layout of plant, trip systems. Permit-to-work.

4. Cigarettes. 5. 6. 7. 8. 9. Smouldering material. Hot process equipment. Distress machinery. Small process fires. Weldings and cutting.

Design. Design and maintenance.

Permit-to-work. Special non-sparking tools are available. Ordinary vehicles excluded from areas of flammable hazard. Security procedures implemented in hazardous areas. This occurs through slow oxidation of a solid.A typical source is oily rags."Good Housekeeping" should prevent this.

10. Mechanical sparks. 11. Vehicles. 12. Arson. 13. Self-heating.


14. Static electricity

This complex problem cannot be properly treated here. The reader is referred to specialist texts such as "Electrostatics in the Petroleum Industry" by Klinkenberg and van der Minne (1958). Electrical equipment to be positioned in these areas have to be built to special standards.In the UK and in many other countries the areas at risk are classified according to the severity of the risk with a different electrical equipment standard for each classification.

15. Electrical equipment.


PotentialSour-ces of Ignition

APPENDIX DThe Properties of Some Hazardous Materials

D.1 FLAMMABLE PROPERTIESThe models presented in Section 4 require upper flammability limits (UFLs) and lower flammability limits (LFLs). Table D. 1 below gives some data for common hazardous materials presented as volume per cent in air. If data are not available for a particular material it is possible to estimate a flammability limit by taking data for a similar material and applying the following: MB LFLA = LFLBMA

where MA and MB are the relevant molecular weights.

Compound Acetone Acetvlene Ammonia Amylene Benzene n-Butane i-Butane Butene-1 Butene-2 Cyclohexane Decane Ethane Ethylene Ethylene dichloride Ethylene oxide Heptane Hexane Hydrogen Methane n Pentane Propane Propylene Toluene Vinyl chloride 2,2-Dimethylpropane 2,3-Dimethylpentane

Limits of flammability Lower (%v/v) Upper (%v/v) 2.6 2.5 15.0 1.8 1.4 1.8 1.8 2.0 1.7 1.3 0.8 3.0 2.7 6.2 3.0 1.2 1.4 4.0 5.0 1.8 2.1 2.4 1.3 4.0 1.3 1.1 13.0 100.0 28.0 8.7 8.0 8.4 8.4 10.0 9.7 7.8 5.4 12.4 36.0 15.9 100.0 6.7 7.4 75.0 15.0 7.8 9.5 11.0 7.0 22.0 7.5 6.8

TABLE D. 1: FlammabilityLimits of Some Common Materials


D.2 TOXIC PROPERTIESDuring the last 10 years, probit equations have been derived for estimating, from dose relationships, the probability of affecting a certain proportion of the exposed population. These have been based almost exclusively on animal test data, which are often very imprecise anyway, and can sequentially they are not very reliable. In particular they do not possess the accuracy which could be ascribed to the fomiula as used in calculations of consequential effect, and they only apply to acute effects of accidental exposures. In recent years, some of the original equations have been subject to much scrutiny and criticism, and this has resulted in alternative equations being proposed. In Table D.2 below are listed the latest, or only, equations available for a variety of toxic gases, but it is important that the origin of each equation is correctly referenced so that the effect of using altemative equations can be quickly established. The difference in results can be exceedingly large in some instances. Probit Equations take the form:Pr = At + Bt In (Cnte)


Pr is the probability function (expressed in units of standard deviation, but with an offset of +5 to avoid the use of negative values) At, Bt, and n are constants, and C is concentration of pollutant to which exposure is made, and is ppm v/v te is the duration of exposure to the pollutant, measured in mninutes.

Note: if the unit of C and/or te are changed, e.g. to mgm/litre v/v, then the values of the constants will change. All units should therefore be quoted.

Material Chlorine Ammonia Acrolein Carbon Tetrachloride Hydrogen Chloride Methyl Bromide Phosgene Hydrogen Fluoride (monomer)

At -5.3 -9.82 -9.93 0.54 -21.76 -19.92 -19.27 -26.4

Bt 0.5 0.71 2.05 1.01 2.65 5.16 3.69 3.35

n 2.75 2.0 1.0 0.5 1.0 1.0 1.0 1.0

Reference DCMR DCMR USCG USCG USCG USCG USCG USCG 1984 1984 1977 1977 1977 1977 1977 1978

TABLE D.2: Toxic Propertiesof Some Materials


Propertiesof Some HazardousMaterials

Bibliography AMERICAN PETROLEUM INTITUTE (1969) Guide for Pressure Relief and Depressuring Systems; New York: API RP 521BRIGGS, G.A (1969) Plume Rise U.S. Atomic Energy Commision, Div. Tech., AEC Critical

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BRIGGS, G.A. (1976) The Lift-Off of a Buoyant Release at Ground Level. BRISCOE, F. and SHAW, P. (1978) Evaporation from Spills of Hazardous Liquids on Land andWater. SRD RI00.

COX, R.A. and CARPENTER, R.J.(1980) Further Development of a Dense Vapor CloudDispersion Model for Hazard Analysis. In: Heavy Gas andRisk Analysis, edited by Sittartwig.

CLANCEY, V.J. (1972) Diagnostic Features of Explosion Damage Sixth Int. Mgt of ForensicScience

COX, B.G. and SAVILLE, G. (eds) (1975) High Pressure Safety Codes; London, ImperialCollege: High Technology Technology Association.

CRANE (1981) Flow of Fluids through Valves, Fittings and Pipes - Metric Edition. Technical CUDE, A.L. (1975) The Generation Spread and Decay of Flammable Vapour Clouds. IChemE Course "ProcessSafety - Theory and Practice",Teeside Polytechnic, Middlesborough, 7-10 July 1975. D.I.P.P.R. (1985) Data Compilation Tables of Properties of Pure Compounds, A.I.CheE.DesignInstitutefor PhysicalPropertyData. New York.

EMERSON, M.C (1986) A new 'unbounded' jet dispersion model. 5th InternationalSymposiumon Loss Prevention andSafety Promotion in the ProcessIndustries, Cannes, September 1986.

ENGLAND, W.G. et al. (1978) Atmospheric Dispersion of LNG Vapour Cloud using SIGMET, a 3-D Time-Dependent Hydrodynamic Computer Model. Heat Transferand FluidMechanicsInstitute, Washington.

FAUSKE, H.K., (1965). The Discharge of Saturated Water through Pipes.CEP Symp. Series 59:

FINNEY, D.J., (1971) Probit Analysis; London,Cambridge Univ. Press. KLINKENBERG, A. and VAN DER MIMNE, J.L. (1958) Electrostatics in the Pertroleum Industry, Amsterdam, Elsevier. LEES, F.P., (1980) Loss Prevention in the Process Industries, London, Butterworths. McADAMS, W.H. (1954) Heat Transmission, 3rd Edition, New York, McGraw Hill. 169

MONIN, A.S. (1962) J. Geographys.Res., 67, 3103. MOORHOUSE, J. and PRITCHARD, M.J. (1982) Thennal Radiation Hazards from Large Pool Fires and Fireballs. A Literature Review. The Assessment of Major Hazards Symposium, Manchester. NIOSH, National Institute for Occupational Safety and Health; Item 37, Washington D.C.: U.S. Govt. Printing Office PASQUILL, F. (1961) The Estimation of the Dispersion of Windbome Meterials. Met. Mag., 901063), 33. SUITTON, O.G. (1953) Atmospheric Diffusion, London: Van Nostrand. ROBERTS, A.F. (1982). "The Effect of Conditions Prior to Loss of Containment in Fireball Behaviour." The Assessment of MajorHazards Symposium, Manchester. TOEGEPAST NATURWETESHAPPELIJK ONDERZOEK (TNO), (197). Methods for the Calculation of the Physical Effects of the Escape of Dangerous Material ("TNO Yellow Book). ULDEN, A.P. van, (1974). "On the Spreading of a Heavy Gas Released near the Ground." 1stInternationalLoss Prevention Symposium, The Hague/Deift.



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ISSN 0253-7494 1 ISBN 0-8213-0779-7