P.

Lettieri

Safety, Hazards and Risks

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Content
History Safety and Loss Prevention Hazards & Risk Analysis Properties of Materials Flammable Chemical - Toxicity Control of Chemical Reactions

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Objectives
Why do we study safety and loss prevention ? Why is it that in the final examination for this course, the question on safety is compulsory? Why does the IChemE make safety the only area in which corporate members MUST have training and experience ? The history of accidents will answer these questions!

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Safety and Sustainable Development

Intensity of exposure

Safety

sustainable development

Health

Environment

Duration of exposure (time)

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Historical Aspects of Safety

1750BC: Code of Laws of Hammurabi Deuteronomy Chapter 22 verse 8 1785: Count Morozzo 1921: Oppau 1966: Aberfan 1974: Flixborough 1976: Seveso 1984: Bhopal Mexico City 1988: Piper Alpha

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Early Health & Safety Law

If a builder build a house and do not make its construction firm, and the house which he has built collapse and cause death of the owner of the house, that builder shall be put to death Hammurabi Law 229 (circa 1750 BC)

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1974: Flixborough

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temporary pipe with dog-leg

Reactor 6

Reactor 4

original connections and flexible bellows

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1988: Piper Alpha

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Accident Pyramid
1 30 300 ?000 Disabling injury Lost time accident Minor Injury Medical treatment Near-misses Property Damage Critical situations Unsafe habits

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Cost of Top 10 Accidents in UK since 1974 (1996 costs M)

Company, Location Texaco/Gulf, Pembroke BP Oil, Grangemouth Laporte Chemicals, Warrington National Freight, Sheffield BASF, Wilton, Teeside J Kelman Transport, Renfrew Amoco, Milford Haven RA Lister, Dursley, Glos Morganite Ceramic Fibres, Merseyside Shell, Ellesmere Port Date 1994 1987 1984 1984 1995 1977 1983 1983 1984 1990 Cost 100M 100M 43M 37M 20M 20M 18M 16M 10M 10M

Source: IChemE Loss Prevention Bulletin, No 140, April 1998

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Cost of Top 10 Accidents Worldwide since 1974 (1996 costs $M)

Location Pasadena, Texas La Mede, France Pampa, Texas Antwerp, Belgium Thessaloniki, Greece Norco, Louisiana Sweeny, Texas Romeoville, Illinois Port Neal, Iowa Sodegaura, Japan Date 1989 1992 1987 1989 1986 1988 1991 1984 1984 1992 Cost $1,456M $458M $396M $356M $300M $293M $264M $241M $182M $172M

Source: IChemE Loss Prevention Bulletin, No 140, April 1998

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What causes an Accident?

Deficient Procedures or documentation Lack of knowledge or training Failure to follow procedures Deficient planning or scheduling Miscommunication Deficient supervision Policy problems

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Prime Responsibilities for Accidents (1981-83)

Senior management Local management Workers Management and Workers Others No one TOTAL % % % % % % 100%

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Fatalities Reported to HSE

1400 1200 1000 800 600 400 200 0 1960

H&SWA 1974

Piper Alpha

1970

1980

1990

2000

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LOSS PREVENTION
Code of Hammurabi Health and Morals Act of 1802 Factories Act 1844 Health and Safety at Work Act 1974

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Health and Safety at Work Act 1974

Duties of the employers: Employers must safeguard so far as is reasonably practicable, the health, safety and welfare of the people who work for them

Duties of the employees: Employees have a duty to take reasonable care to avoid injury to themselves or to others by their work activities

Duties of manufacturers and suppliers: Designers, manufacturers, importers or suppliers of articles or substances for use at work must ensure that, so far as reasonably practical, they will be safe when used

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Establishing a Safe System Of Work

It is managements duty to:
Define the safe system of work Train people in that safe system Observe that they are working in this method

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LOSS PREVENTION

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Loss Prevention
Definition: A systematic approach to preventing accidents or minimising their effects Prevent the unwanted event from happening

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Accident rate

Recent Approaches to Safety

Design standards Plant inspections

Technical Safety Safety Audits

Human factors Performance indicators Management Systems Culture

?
2000s

1950s

1960s

1970s

1980s

1990s

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Safety Management
Plan Organise Control Monitor Review

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Policy
Supporting Human Resource Development Minimising Financial Losses Recognising that accidents and ill health result from failings in management control Recoginsing that the development of a culture supportive of H&S is necessary to achieve adequate control over risks Ensuring a systematic approach to the identification of risks and allocation of resources to control them Supporting quality initiatives aimed at continuous improvement

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Loss Prevention and Total Quality Management

Commitment to the customer, the employee and the community by the senior management team Commitment to the importance of human factors, covering the job, the individual and the organisation Commitment to prevention of loss whether it is of product, of people or of customers Commitment to continuous improvement of the product as well as the work situation Commitment to setting standards and measuring the performance of individuals or groups against standards

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Organising for Loss Prevention Operation Plan

Safety Improvement Plans are developed Meetings are attended Decisions made are implemented

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Human Factors
Human Error
Slips / Lapses of Attention Mistaken Actions Wrong Perceptions Violations

Operator Response
Routine operator action Operator intervention in an emergency
Operator hears alarm Operator recognises what the alarm means Operator decides what action is required Operator performs the action

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Controlling for Loss Prevention Standards Measure Compliance

Measurement Results Plan for Loss Prevention

Evaluate

Work completed satisfactorily

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key elements of a safety management system

Policy

Organising

Auditing

Planning and Implementing Measuring Performance Reviewing Performance

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Legislation
Old-Style Legislation
Prescriptive Detailed rules and regulations What must be done Do it anyway

New-Style Legislation
Based on likelihood of harm done Framework rules with guidelines How it must be managed Identify anything that causes harm and likelihood of it occurring first, rank them and prioritise actions accordingly

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Safety Culture
demonstrate commitment to safety and thus generate high levels of motivation and concern for health and safety throughout the organisation adopt good communications between all levels of the workforce and thus provide a bridge across the management hierarchy boundaries accept that the promotion of safety culture is a long-term strategy which requires sustained effort and interest adopt a formal health and safety policy, supported by adequate codes of practice and safety standards balance safety and production or service goals and stress that health and safety is equal to other business objectives evaluate safety systems to provide information feedback with a view to developing ideas for continuous improvement

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HAZARD and RISK

HAZARD
Anything that can cause harm A physical situation with a potential for human injury, damage to property, damage to the environment or some combination of these

RISK
The likelihood that someone will be harmed by the hazard The likelihood of a specified undesired event occurring within a specified period

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Safe Systems of Work

we have to identify the hazard we evaluate the risk we establish a control system to minimise the risk

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Risk Assessment
each job may be broken down into tasks the potential for causing loss determined the method of working detailed.

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Identify Hazards

Estimate Risks

Assess Tolerability

Management Intervention

Control & Review

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Term FAILURE HAZARD

Definition

Example

Deviation from the normal design Defective Welds intent or operating standard A situation with the potential to cause death, injury, damage, losses or liabilities Operating Pressure too high

ACCIDENT

An unplanned, uncontrolled event Pipeline dug up by excavator giving rise to death injury, ill-health, damage or loss Explosion of gas cloud Fatal, Serious, Minor

CONSEQUENCE An outcome resulting from an accident SEVERITY A measure of the Consequence

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Assessment of a risk
involves the rating of two factors which affect the risk
1. the severity of the hazard 2. the likelihood of an occurrence of harm from the hazard

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Increasing Likelihood frequency yr-1 <10-6 Never heard of in industry 10-6-10-4 Heard of in industry 10-4-10-2 10-2-1 >1 Happens several per year in our location Incident Happens has several occurred per year in our in our company company

Consequence Rating: Severity 0: No injury 1: Slight injury 2: Minor injury 3: Major injury 4: Single Fatality 5: Multiple Fatalities

Inc rea sin gR i sk

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Frequency

Consequence

Risk

How likely is it that the hazard will cause an accident?

If an accident occurs, how severe are the consequences?

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FARs: Fatal Accident Rates

number of deaths per 1000 workforce during a working lifetime 105 hours
Industry Chemical UK Industry (factory work) Coal Mining Offshore Oil and Gas Steel Erectors FAR 2 4 8 62 70 Other Activities Staying at home Rail Travel Car Travel Helicopter travel Rock Climbing FAR 1 4 30 500 4000

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Risk per 109 km traveled in UK, 1986-90

UK scheduled airline passengers Rail passengers Car drivers and passengers Pedal cyclists Pedestrians Motor cycle riders 0.2 1.1 4.4 50.0 70.0 104.0

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Direct Costs

Indirect Costs
Management Time Compensation Claims Increased Insurance Costs Business Interruption Loss of Good Will

The Cost Iceberg

8 - 36

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Level of Risk
Tolerability Intolerable Level

ALARP
A As sL Low ow A As s R Reasonably easonably P Possible ossible

Risk cannot be justified on any grounds

Tolerable Tolerable if ALARP Risk is undertaken only if a benefit is desired

Only if risk reduction is impracticable or if its cost is grossly disproportionate to the improvement gained

Tolerable
If cost of reduction would be disproportionate to the improvement gained

Broadly Acceptable

Negligible Risk

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ALARP
TECHNOLOGY Intolerable Level A As sL Low ow A As s R Reasonably easonably P Possible ossible

Risk Reduction regardless of cost

Relevant Good Practice plus Tolerable if ALARP Risk Reduction Measures plus Gross Disproportionation

Broadly Acceptable

Relevant Good Practice

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Objectives
To identify the hazards To decide on the likelihood or damage To determine action to be taken to control adequately To comply with Health & Safety Legislation

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Managing Risk
HAZARD Solvent base paint system (no alternative for particular application) Exposure to solvent Paint section off-site in a controlled environment if possible Brush apply at site Ensure good ventilation area Use respirator and protective clothing

RISK CONTROL MEASURES

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Identification of Hazards
HAZard and OPerability Study - HAZOP Fault Tree Analysis - FTA Safety Analysis Function Evaluation SAFE Charts Check Lists / What if Analysis

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Risk Assessment
www.hse.gov.uk
1. Look for the hazards 2. Decide who might be harmed, and how 3. Evaluate the risks and implement control measures where necessary 4. Record you findings 5. Review your assessment and revise it if necessary

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FAULT TREE ANALYSIS

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Fault Tree Analysis

Technique to find a sequence of faults and causes leading to a hazardous event
LOGIC symbols
OR gate

EVENT symbols
Basic Event Combination Event

AND gate Fault Event - not required to be developed further

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Miss start of Lecture

Bike stolen

Collision Damage to Bike

Flat Tyre on Way to UCL

Minor Collision Damage to Bike

Driver cuts off cyclist

Potential Calamity

Cannot Avoid Car

Ride Bike to UCL

Driver Hits Bike with Door

Car Encountered

Ride Bike to UCL

Driver Does Not See Bike

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QUENCH TANK V1 close button

L1
V2 V2 open button

Inlet

L2

T1

Temperature Alarm

V1

T2

DAMAGE TO REACTOR DUE TO HIGH TEMPERATURE

REACTOR L3 Outlet

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The Problem
An unstable exothermic reaction is being carried out in a reactor protected against a runaway reaction with a quench system as shown in Figure. Two independent sensors T1 and T2 continuously monitor the reaction temperature. The quench tank outlet valve V2 opens automatically when T1 detects a certain increase in temperature. T2 activates an alarm in the control room independently to alert the operator to a possible loss of control of the reaction. When the alarm sounds the operator should press a button to close valve V1 to stop the reactor feed. When the operator hears the alarm he is also instructed to press the button that opens the quench tank outlet valve in the event that sensor T1 fails to operate.

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Damage to Reactor due to High Temperature

No Flow in L1

Valve V1 Remains open

Quench Tank Empty

Valve V2 does not open

Valve V2 not Initiated

V2 Fails to Open

Operator fails to initiate V2

T1 fails to initiate V2 T1 Fails to detect Temp rise

Operator fails to obey alarm and Open V2

Alarm fails to Alert Operator

Alarm Fails Off

T2 Fails to detect Temp rise

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FLAMMABLE PROPERTIES
The Fire Triangle
All three elements must be present at the same time to have a fire. Take any of these away, and you will not have a fire or the fire will be extinguished.

a He

Ox yg e

Fuel

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Flash Point
Temperature at which the material will just catch fire at atmospheric pressure if a source of ignition is applied. Temperature at which the vapour pressure of the material equals the lower flammable limit. Typical Values:hydrogen methane n-hexane n-octane gasoline diesel C extremely low very low -22 13 -38 43 to 88

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Flammable Limits
Lower Flammable Limit is that concentration in
air of a flammable material below which combustion will not propagate. (lower explosion limit)

Upper Flammable Limit is that concentration in

air of a flammable material above which combustion will not propagate. Typical values:Vapour hydrogen methane propane natural gas Volume % Vapour in Air Lower Limit 4 5.3 2 3.8 - 6.5 Upper Limit 75 14.0 9.55 13.0 17.0

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Variation of Flammability Characteristics with Change of Temperature

Concentration
Boiling point
mable limit m a fl r e p p U

Vapour pressure curve Flammability range

Lower f lamm

Autoignition

Flash point

able lim it Autoignition temperature

Temperature

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Autoignition Temperature
The minimum temperature at which that material will initiate and sustain in air a combustion process without the provision of a source of ignition.
Typical values:pentane 1.5 v/v % pentane 3.75 v/v % pentane 7.65 v/v % diesel oil gasoline ( C) 548 502 476 257 456

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Sources of Ignition
Mechanical
Friction Missiles

Thermal
Hot surfaces Self-heating Flames Engines

Electrical
Electrical Current Electrostatic Lightning Stray Currents Radio frequency

Chemical
Peroxides Polymerisation Spontaneous Reactions with other substances Thermite reaction Unstable substances Decomposition

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Types of Fire and Deflagration

Pool Fire
occurs when liquid is spilt onto a surface and the vapour ignites

Unconfined Vapour Cloud Explosion

An explosion in the open air of vapour which is not confined by walls, vessels or other equipment.

Jet Fire
occurs when a vessel or pipe under pressure leaks from a small hole causing a jet of liquid or vapour to be emitted and which ignites

BLEVE
Boiling Liquid Expanding Vapour Explosion Occurs when a vessel containing a liquid at a temperature above its atmospheric boiling point ruptures and ignites.

Fire Ball
a fire burning sufficiently rapidly for the burning mass to rise into the air as a cloud or ball

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Water: reduces heat input Remote operated depressurising valve: reduces pressure in vessel Insulation: reduces heat input

Fire relief valve: set to operate before weakened walls rupture No liquid to absorb heat, walls may overheat and fail

Detector

Boiling liquid absorbs heat, keeps walls cool

Insulated supports

Sloping ground: prevents liquid collecting

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Dust Explosions
A dust explosion is very similar to a gas or vapour cloud explosion, i.e. when a volume of a flammable mixture is ignited, resulting in a rapid pressure increase and fire moving through the cloud. A dust explosion occurs when a combustible material is dispersed in the air forming a flammable cloud and a flame propagates through it.

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Dust Explosions
The dust must be combustible The dust must be capable of becoming airborne The dust must have a size distribution capable of flame propagation The dust concentration must be within the explosive range An ignition source must be present The atmosphere must contain sufficient oxygen to support and sustain combustion

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Material Safety Check List

Flash Point Flammability Range Autoignition Temp Composition Stability & Reactivity Toxicity Corrosion Heat of Combustion

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Material Safety Data Sheet

1. Composition/ Information on ingredients 2. Chemical Product 3. Hazards Identification 4. First Aid 5. Fire Fighting Measures 6. Accidental Release Measures 7. Handling and Storage 8. Exposure Controls/ Personnel Protection 9. Physical and Chemical Properties 10. Stability and Reactivity 11. Toxicological Information 12. Ecological Information 13. Disposal Consideration 14. Transport Information 15. Regulatory Information MSDS Example: cyclohexane

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Chemical Properties
Chemical hazards
Asphyxiant Narcotic Toxic Irritant Sensitising Corrosive

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Chemical Properties
Asphyxiant
Asphyxia is caused by the lack of oxygen reaching the blood and hence the brain.

Narcotic
When the oxygen has been displaced by hydrocarbon vapour, the physiological effect may be complicated since the effects of asphyxia may be combined with the effects of narcotic, irritant and/or toxic vapour.

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Definition of terms
Toxicity
Acutely toxic - have an immediate effect on a person Chronically toxic - have an effect after prolonged exposure to small quantities.

Very Toxic
A substance which if it is inhaled or ingested or it penetrates the skin may involve extremely serious acute or chronic health risks and even death.

Toxic
A substance which if it is inhaled or ingested or it penetrates the skin may involve serious acute or chronic health risks and even death.

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Definition of terms
Irritant
A non-corrosive substance which, through immediate, prolonged or repeated contact with the skin or mucous membrane, can cause inflammation.

Sensitiser
Substances or agents which on first exposure may or may not cause local skin effects. Initiates a defensive-type mechanism within the body which is triggered to produce reactions on second or subsequent exposure.

Corrosive
A substance which on contact with living tissues destroy them. Burning and/or blistering, i.e. direct chemical contact areas as in the nose and throat and on the skin.

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Definition of terms
Carcinogenic
A substance which if it is inhaled or ingested or if it penetrates the skin may induce cancer in man or increase its incidence.

Teratogenic
A substance which if it is inhaled or ingested or it penetrates the skin may involve a risk of subsequent non-hereditable birth defects in offspring.

Mutagenic
A substance which if it is inhaled or ingested or it penetrates the skin may involve a risk of hereditable genetic defects.

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LD50
LD50: Lethal dose for 50% fatality (usually on rats) within specified time period - often 14 days.

Median Lethal Concentration (LD50)

Absorbed orally in rat mg kg-1 (4 hrs) Category Very Toxic Toxic Harmful 25 25 200 200 - 2000 Absorbed percutaneously in rat or rabbit mg kg-1 50 50 400 400 2000 Absorbed by inhalation in rat mg litre-1 0.5 0.5 2 2 - 20

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Occupational Exposure Limits: OELs

maximum concentrations in air averaged over a particular time period
Long term limit - used for substances producing chronic effects Short term limit - for substances producing acute effects Long term limit Short term limit 8 hrs 15 min Notes ppm Acetic Acid Acetic Anhydride Acetone 64-19-7 108-24-7 67-64-1 10 750 mg m-3 25 1780 ppm 15 5 1500 mg m-3 37 20 3560

Substance

CAS No

Methyl isocyanate

624-83-9 0.02

0.047

Skin

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USA: Threshold Limit Values: TLVs

TLV
refers to airborne concentrations

TLV-TWA
Time Waited Average
8 hour working day for 40 hours per week repeatedly exposed without adverse effect.

TLV-STEL
Short Term Exposure Limit
for 15 minutes max. with no more than 4 excursions during an 8 hour day without adverse effect.

TLV-Ceiling
The concentration which must not be exceeded.

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COSHH Control Of Substances Hazardous to Health

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To comply with COSHH:

1. Assess the risks 2. Decide what precautions are needed . 3. Prevent or adequately control exposure. 4. Ensure that control measures are used and maintained. 5. Monitor the exposure 6. Carry out appropriate health surveillance 7. Prepare plans and procedures to deal with accidents, incidents and emergencies 8. Ensure employees are properly informed, trained and supervised.

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What is a substance hazardous to health under COSHH?

Substances or mixtures of substances classified as dangerous to health under the Chemicals (Hazard Information and Packaging for Supply) Regulations 2002 (CHIP). Substances with occupational exposure limits Biological agents Any kind of dust Any other substance which creates a risk to health

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Material Safety Data Sheet

1. Composition/ Information on ingredients 2. Chemical Product 3. Hazards Identification 4. First Aid 5. Fire Fighting Measures 6. Accidental Release Measures 7. Handling and Storage 8. Exposure Controls/ Personnel Protection 9. Physical and Chemical Properties 10. Stability and Reactivity 11. Toxicological Information 12. Ecological Information 13. Disposal Consideration 14. Transport Information 15. Regulatory Information

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Safety Symbols
(Highly) Flammable

Biohazard Dangerous When Wet Harmful

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Sources of information UK: Heath and Safety Executive

www.hse.gov.uk source of safety data source of guidance e.g. OELs publications on specific hazards
arsenic, asbestos

USA: Environmental Protection Agency

www.epa.gov

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RUNAWAY EXOTHERMIC REACTIONS

A chemical reaction invariably involves an energy change Heat is either absorbed or released If heat is given out the reaction is said to be exothermic An exothermic reaction can lead to thermal runaway, which begins when the heat produced by the reaction exceeds the heat removed The surplus heat raises the temperature of the reaction mass, which causes the rate of reaction to increase This in turn accelerates the rate of heat production

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RUNAWAY EXOTHERMIC REACTIONS

runaway Rates of Heat Generation & Heat Transfer heat transfer stable heat generation Temperature
Q = UAT

critical temperature

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Causes for Runaway Reactions

In batch and continuous operations Mixing wrong materials Contanimation Decomposition particulalrly becaused of over-heating

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The Essential Features for Planning a Batch Chemical Reaction

correct charging of materials reactor cooling agitation control temperature pressure training

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Correct Charging of Materials

materials used must be charged in the correct amounts and in the correct order problems:wrong material being added wrong amounts of material being added including the catalyst wrong order of charging may materially affect the reaction wrong temperature used for the charging period wrong rate of charging

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Reactor Cooling
heat generated by the reaction must be removed by the cooling system chosen problems: The wrong temperature for the reaction is used so that the rate of heat generation is greater than the cooling capacity. The critical temperature has been exceeded The cooling capacity of the system is unable to cope with increased rate of heat generation The failure of the cooling system

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Agitation
maintains all materials in close contact with one another and assists in temperature control problems: failure of agitation by power failure or agitator failure causing solids to settle and loss of cooling capacity. agitator causing vortex and temperature probe coming out of liquid. failure to restart agitator after sampling etc.

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Temperature and Pressure Control

Temperature
control throughout the reaction is crucial problems: wrong temperature due to probe not covered or too short wrong temperature due to control misaligned or other instrument faults wrong strategy of reaction control

Pressure
pressure in the reactor is a result of the temperature change and/or the release of gases. problems: the rate of pressure rise is greater than that which can be catered for by the venting system vent design inadequate

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Training
one of the most important areas but one which the design engineer can influence by ensuring the design philosophy is contained in the procedures for operating the plant problems: operators are not properly trained operating instructions do no not reflect the design intent the combination of factors for the reaction involved and simple failures of safety back-up systems contributed to the severity of incidents

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Literature
IChemE: Guide to Chemical Reaction Hazards IChemE: Relief Systems Handbook IChemE: provides also a list of consultants, experts active in this field