FIRE AND SAFETY

ENGINEERING

ZSUZSANNA MOMADE
DEPARTMENT OF CHEMICAL ENGINEERING
KNUST
2023
TABLE OF CONTENT
REFERENCES ..…….4
1. INTRODUCTION ………5
1.1 Historical background ......................................................... 5
1.2 Definitions........................................................................... 8
1.3 Accident and loss statistics................................................ 11
1.4 The nature of the accident process ................................... 16
1.5 Inherent safety................................................................... 20
1.6 Risk management and insurance ...................................... 21

2. FIRE AND EXPLOSION HAZARD ………23

2.1 The fire triangle.................................................................. 23
2.2 Classes of fire.................................................................... 25
2.3 Definitions.......................................................................... 25
2.4 Flammability characteristics of liquids and vapours........... 32
2.5 Limiting oxygen concentration and inerting ....................... 38
2.6 Flammability diagram ........................................................ 39
2.7 Ignition energy ................................................................... 40
2.8 Autoignition........................................................................ 41
2.9 Auto-oxidation.................................................................... 43
2.10 Adiabatic compression ...................................................... 43
2.11 Ignition sources ................................................................. 43
2.12 Sprays and mists ............................................................... 44
2.13 Explosions ......................................................................... 45
2.14 Missile damage.................................................................. 56
2.15 Vapour cloud explosion (VCE) .......................................... 56
2.16 Boiling liquid expanding vapour explosion (BLEVE).......... 58

3. DESIGNS TO PREVENT FIRES AND

EXPLOSIONS ………60
3.1 Inerting............................................................................... 60
3.2 Static electricity.................................................................. 64
3.3 Controlling static electricity ................................................ 75
3.4 Explosion-proof equipment and instruments ..................... 82
3.5 Ventilation.......................................................................... 84
3.6 Sprinkler systems .............................................................. 84
3.7 Reliefs................................................................................ 85
3.8 Emergency fire fighting...................................................... 87
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 3.9 Chemical reactivity ............................................................ 90
3.10 Lessons learned from accidents........................................ 94

4. HAZARDOUS MATERIALS .........96

4.1 Classification of hazardous materials and safety labels .... 96
4.2 Toxic materials ................................................................ 103
4.3 Corrosive materials.......................................................... 108
4.4 Asphyxiants ..................................................................... 109
4.5 Biological hazard ............................................................. 109

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REFERENCES
Crowl, D.A. and Louvard, J.F. (2011) Chemical Process Safety, Fundamentals
with Applications 3rd ed., Prentice Hall International series

King, R.W. and Magid, J. (1982) Industrial Hazards and Safety Handbook, 3rd
(Revised) impression, Butterworth Scientific, London

Turns, S.R. (2000) An Introduction to Combustion: Concepts and Applications

2nd ed., McGraw Hill Companies Inc., USA

Quintiere, J.G (2006) Fundamentals of Fire Phenomena, John Wiley & Sons
Ltd., England

Nolan, D.P. (2011) Handbook of Fire and Explosion Protection Engineering

Principles for Oil, Gas, Chemical and Related Facilities, 2nd ed., Elsevier Inc.

Hearn, G. (2002) Static Electricity, Guidance for Plant Engineers [online]

Glor, M. (2003) Ignition hazard due to static electricity in particulate processes,

Powder Technology 135-136, p.223-233 Elsevier [online]

Glor, M. (1999) Electrostatic Ignition Hazards Associated with Flammable

Substances in the Form of Gases, Vapors, Mists and Dust, 10th International
Conference on Electrostatics, Cambridge, England, March 28-31, 1999 in
Taylor, E.D.M. (ed) Electrostatics pp. 199-206, OP Publishing Ltd. Bristol,
England [online]

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1. INTRODUCTION
Fire was present at the creation of the Universe. It has been a part of us from the
beginning. The ancient Greeks believed that fire was one of the four basic elements
that composed of all things in the universe (fire, water, earth, and air). The theory was
suggested around 450 BC. Fire is not, in fact, a substance. When you gaze at the
flames, you are observing not an object, but a process — a chemical reaction.

Reliance on fire for warmth, light, cooking, and the engine of industry has faded from
our daily lives of today, and therefore we have become insensitive to the behaviour of
fire. Mankind has invested much in the technology to maintain fire, but relatively little
to prevent it. Dramatic disastrous fires have been chronicled over recorded history, and
they have taught more fear than complete lessons.

The cost of fire (property loss, fire department operations, burn injury treatment,
insurance cost, and productivity loss) is currently estimated at 0.875% of the Gross
Domestic Product (GDP) or about $102 billion in the USA. The current US defence
spending is at 3.6% of GDP. The fire cost per GDP is about the same for most
developed countries, ranging from 0.2-1.2% with a mean for 23 countries at 0.81%.
Making the work environmentally safer was found to be less costly than paying
compensation for injuries, fatalities, government fines, and higher insurance premium.

Improvements in safety are often the sequel to some traumatic experience. During the
1950s to 1970s a number of industry-specific safety laws were enacted throughout the
developed world.

Chemical industry is entering an era of more complex processes: higher pressure, more
reactive chemicals, and exotic chemistry. More complex processes require more
complex safety technology. The development and application of safety technology is
actually a constrain on the growth of chemical industry.

Since the 1950s, significant technological advances have been made in chemical
process safety. Today safety is equally important to production.

The word “safety” used to mean the older strategy of accident prevention through the
use of hard hats, safety shoes, and a variety of rules and regulations. The main
emphasis was on worker safety. Much more recently, “safety” has been replaced by
“loss prevention”. This term includes hazard identification, technical evaluation, and
design of new engineering features to prevent loss.

1.1 Historical background

The oil industry started in Azerbaijan near Baku, where oil seeps flowed freely for
many centuries B.C. The first modern oil well was drilled near Baku in 1848.
Therefore, the modern petroleum industry is over 160 years old.

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The world first commercial oil well was drilled in Poland in 1854. The first wells in
America were drilled in 1858 in Ontario, Canada and 1859 in Pennsylvania, in the
USA.

•
BAKU

The map of South Caucasus

The first oil wells were followed by first refineries and first sizable oil spills.

Hydrocarbon fires were a fairly common sight at early oil field. They were accepted as
part of the perils of early industry and little effort was made to stem their existence.
Usually very limited safety features for fire or explosion protection were provided.
The industry was known as “risky”.

The hydrocarbon and chemical industry have traditionally been reluctant to

immediately invest capital where direct return on the investment to the company is not
obvious and apparent. Additionally, fire losses were small up to the 1950s. This was
due to the small size of the facilities and the relative low value of oil, gas, and
chemicals to the volume of the production. The use of gas was also limited in the
1900s, as its value was very low. Typically, production gas was immediately flared or
the well was capped and considered an uneconomical reservoir. Since gas
development was limited, large vapour cloud explosions were rare and catastrophic
destructions were unheard of.

The magnitude of incidents of fires, explosions, and environmental pollution has

grown parallel to the growth of the industry.

After the Second World War, large integrated petroleum and petrochemical complexes
were constructed, the development and use of gas deposits increased, and the oil and
gas prices rose in the 1970s. This led to the sky-rocketing of the value of petroleum
products and facilities. It also meant that the industry was awakened to the possibility
of large financial losses if a major incident occurred.

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 Nominal
Real (2014 dollar)

Crude oil prices since 1861

Average cost to produce one barrel of oil in

top producing countries in 2015 in US$/barrel

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Fire losses greater than US$50 million were first reported in 1974 (Flixborough in the
UK). In 1988, the cost just to replace the Piper Alpha platform was over $1 billion. In
2010, the Deepwater Horizon/BP accident cost BP $19 billion; BP also has made
provision of $41 billion to pay the damages from the oils spill; and BP group lost
about 70 billion dollars in market value (07 Aug. 2011, Economics News Paper).

The development of loss prevention philosophies and practices were not developed
within the industry until major catastrophic and financially significant incidents of the
1980s and 1990s.

It is only the last several decades that most industries have understood and
acknowledged that fire and explosion protection measures may also be operational
improvement measures, as well as means of protecting a facility against destruction.
Nowadays safety features should hopefully promulgate the design and arrangement of
all petroleum and chemical facilities.

1.2 Definitions
Accident: is the occurrence of a sequence of events that produce unintended injury,
death, or property damage.

Incident: is the loss of containment of material or energy; not all events propagate into
incidents; not all incidents propagate into accidents.

Safety (or loss prevention): is the prevention of accidents through the use of
appropriate technologies to identify the hazards of a chemical plant and eliminate
them before an accident occurs.

Hazard: a chemical or physical condition that has the potential to cause damage to
people, property, or the environment.

Risk is the chance or probability that a person will be harmed if exposed to a hazard
(OSHA).

Risk is the potential of loosing something of value (such as health, social status,
financial wealth, or emotional well being).

There are economic risk, health risks, safety risks, environmental risks, operational
risks, market risks, mortality risks etc. Any human endeavour carries some risk, but
some are much riskier than others. Insurance is a risk treatment option, which involves
risk sharing.

Risk perception is the subjective judgement people make about the severity or
probability of a risk, and may vary from person to person.

As risk carries so many different meanings, there are many formal methods used to
assess or to “measure” risk.

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Quantitative definition of risk uses statistical theory to calculate risk:

Risk   (probability of the accident occuring) x (expected loss in case of the accident)
for all
accidents

That is risk is a measure of human injury, environmental damage, or economic loss in

terms of both accident likelihood and the magnitude of the loss or injury.

Risk analysis: is the development of a quantitative estimate of risk based on

engineering evaluation and mathematical techniques for combining estimates of
incident consequences and frequencies.

Risk assessment: is the process by which the result of a risk analysis is used to make
decisions, either through a relative ranking of risk reduction strategies or through
comparison with risk targets.

Chemical plants contain a large variety of hazards:

(1) Mechanical hazards, that cause worker injuries from tripping, falling, or
moving equipment
(2) Chemical hazards: these include fire and explosion hazards, reactivity hazards,
and toxic hazards.
(3) Physical hazards: these include ambient heat, burns, noise, vibration, sudden
pressure changes, radiation, and electrical shock.
(4) Biological hazards
(5) Ergonomic hazards: Ergonomic hazards occur when the type of work, body
position and working conditions put strain on the body. If the physical,
psychological, or environmental demand on workers exceed their capabilities, an
ergonomic hazard exists, which may lead to physiological or psychological stress
in individuals. This may lead to further major incidents because the individual
cannot perform properly under stress during critical periods of plant operation.

They are hard to spot since the person not immediately notices the strain on his
body or the harm that these hazards pose. Short term exposure may result in a
“muscle sore”.

Ergonomic hazards include:

 improperly adjusted work stations and chairs
 frequent lifting
 awkward movements, especially if they are repetitive
 awkward working positions and body postures (prolonged bending, reaching,
squatting, or twisting)
 repetitive movements
 having to use too much force
 vibration
 static load
 improperly designed tools and equipment
 thermal comfort (too cold or too hot working environment increases fatigue)
 noise
 work stress (monotonous tasks, inadequate breaks, poor organization, ...)

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 Symptoms of ergonomic disorders are most common in the back, hands, arms,
elbows, neck, and shoulders. They include soreness or pain, stiffness, swelling,
loss of coordination, numbness, tingling, unexplained weakness, fatigue and
drowsiness.

The most effective means of implementing safety programs is to make it everyone’s

responsibility in a chemical process plant. The older concept of identifying a few
employees to be responsible for safety is inadequate by today’s standards. All
employees have the responsibility to be knowledgeable about safety and to practice
safety.

A good safety program eliminates the existing hazards as they are identified, whereas
an outstanding safety program prevents the existence of a hazard in the first place.

The common management systems directed to eliminating the existence of hazards

include:
 safety reviews,
 safety audits,
 hazard identification techniques,
 checklists, and
 proper application of technical knowledge.
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Engineers are responsible for minimizing losses and provide a safe and secure
environment for the company’s employees.

1.3 Accident and loss statistics

Accident and loss statistics are important measures of the effectiveness of safety
programs. These statistics are valuable for determining whether a process is safe or
whether a safety procedure is working effectively.

Statistical methods are available to characterize accident and loss performance.

However these statistics are only averages and do not reflect the potential for single
episodes involving substantial losses.

All accidents have causes and about 99% are preventable!

Causes can be:

 Immediate causes (or direct causes) — the immediate events or conditions
that cause the accident. (e.g. open wrong valve; dust)
 Underlying causes (or contributory causes or indirect causes) — they are
events or conditions which themselves did not cause harm but
made significant contribution to an accident by increasing its
likelihood or severity. (e.g.
 Root causes — these are factors, mostly aspects of safety management
performance, if corrected, would prevent the recurrence of the
same or similar accidents.

By only addressing immediate and underlying causes, you allow the fundamental
deficiencies to remain and make recurrence more likely.

The main causes of accidents or failures:

 ignorance
 economic considerations
 oversight or negligence
 unusual occurrences

Ignorance:
 Incompetent design, construction or inspections occur
 Supervision or maintenance occurs by personnel without the necessary
understanding
 Assumption of responsibility by management without an adequate
understanding of risk
 There is lack of precedent
 There is lack of sufficient preliminary information
 Failure to employ competent Loss Prevention professionals

Economic considerations:
 Initial engineering and construction costs for safety measures appear
uneconomical
 Operation and maintenance costs are unwittingly reduced to below what is
necessary
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 Oversight and negligence:
 Unethical behaviour occur
 Professional engineers and designers commit errors
 Shortcuts
 Overconfidence of workers
 Neglecting safety procedures
 Mental destruction from personal life

It is seldom that a single cause on its own results in an accident. Usually there is a
combination of causes. Accident statistics are important measures of the effectiveness
of safety programs.

Example:
An employee is injured by items falling off shelving and striking him causing injury.
The items falling off the shelves could be the immediate cause.
Underlying causes could be poor maintenance of the shelving and/or incorrect stacking of
materials on the shelves.
The root cause is the failure to supervise the shelving maintenance programme and the
stacking of the materials.

Example: Consider the following accident record

Date and Time of 18/03/2018 16:40
Incident
Site Alternative location, 123 Anywhere Street
Site Address 123 Anywhere Street
Anywherecity
Location of Incident Warehouse
Type of Incident Major injury / Hit by a moving, flying or falling object
Description what An office worker has decided to leave work slightly earlier than normal 2 pm.
happened Instead of using the designated and marked walkway, he decided to take a
short-cut across the warehouse, through the aisles of pallet racking to an exit
via a loading bay.
While he was doing this a colleague was driving a forklift and was busy picking
some goods. In driving by the aisles of pallet racking he suddenly saw his
colleague appear and applied the brakes firmly. While doing this the forklift
truck skidded on an oil spillage and the load fell from the forks and struck the
office worker with significant force.
The office worker sustained a fractured arm and a badly bruised leg.

Immediate causes:
 Load from forklift struck employee
 The forklift truck skidded and the load tipped
 The forklift truck was going too fast
 The driver had to break sharply
Underlying causes:
 A patch of oil on the warehouse floor
 The unexpected appearance of the pedestrian in a truck zone
 Employee took short-cut across warehouse
 Poor maintenance of the forklift truck
Root causes:
 Poor practice and supervision of the admin employee
 Poor work practice and supervision of the driver
 Lack of supervision of the company maintenance programme
 Poor implementation of company Health and Safety Policy and Procedures

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Personal injuries can be:
 minor injuries (having no permanent effects and leading to less than 3 days off
work)
 major injuries (leading to 3 or more days off work)

Shift work, unusually long working hours, and piece-rate systems are all contributory
causes of personal errors, which can lead to accidents. Both overtime and shift work
are favoured by workers and managements. Workers get more money, management
make greater use of existing manpower, while shift working allows fuller
implementation of plant. However, efficiency in these circumstances fall and accident
rates increase.

Property damage and loss of production must also be considered in loss prevention not
only injuries of workers. “No damage” accidents are frequently called “near misses”
and provide a good opportunity for companies to determine that a problem exists and
to correct it before a more serious accident occurs. It is frequently said that “the cause
of an accident is visible the day before it occurs.” Inspections, safety reviews and
careful evaluation of near misses will identify hazardous conditions that can be
corrected before real accidents occur.

Safety has an optimal level of activity beyond which there are diminishing returns. If
initial expenditures are made on safety, plants are prevented from blowing up and
experienced workers are spared. This results in increased returns because of reduced
loss expenditure. If safety expenditures increase, then the return increases more, but it
may be not as much as before and not as much as achieved by spending money
elsewhere. If safety expenditure increases further, the price of the product increases
and sales diminish. Indeed, people are spared from injury, but the cost is decreased
sales. Finally, even higher expenditures result in uncompetitive product pricing: the
company will go out of business. Each company needs to determine an appropriate
level of safety expenditures. This is part of risk management.

1
Fatality

30
Serious injuries

300
Minor injuries

3,000
Near misses

300,000
At risk behaviour can result in...

The accident pyramid

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In 2003, ConocoPhillips Marine conducted a study demonstrating a large difference in
the ratio of serious accidents and near misses. The study found that for every single
fatality there are at least 300,000 at-risk behaviors, defined as activities that are not
consistent with safety programs, training and components on machinery. (These
behaviors may include bypassing safety components on machinery or eliminating a
safety step in the production process that slows down the operator.) With effective
machine safeguarding and training, at-risk behaviors and near misses can be
diminished. This also reduces the chance of the fatality occurring, since there is a
lower frequency of at-risk behaviors.

We cannot eliminate risk entirely. Every chemical process has a certain amount of risk
associated with it. The acceptable risk has to be determined during the design stage.
That is, are the risks greater than the normal day-to-day risks taken by individuals in
their non-industrial environment?

There are three commonly used statistics:

 OSHA incident rate
 FAR (fatal accident rate)
 fatality rate, or death per person per year

All these methods report the number of accidents and/or fatalities for a fixed number
of workers during a specified period.

OSHA stands for Occupational Safety and Health Administration of the US

government.
OSHA incident rate
Incident rate: is the number of occupational injuries and/or illnesses or lost workdays
per 100 full-time employees.

Lost workday: is the number of days during which the employee would not work
after the incidence (not including the day of incidence).

The OSHA incident rate is based on cases per 100 worker years. A worker year is
assumed to contain 2000 hours (50 work week/year x 40 hours/week). The OSHA
incident rate is therefore based on 200 000 hours of worker exposure to a hazard. It is
calculated from the number of occupational injuries and illnesses and the total number
of employee hours during the applicable period:

OSHA incident rate Number of injuries and illnesses

= x 200 000
(based on injuries and illnesses) Total hours worked by all employees
during period covered

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An incident rate can also be based on lost workdays instead on injuries and illnesses:

OSHA incident rate Number of lost workdays

= x 200 000
(based on lost workdays) Total hours worked by all emplyees
during period covered

FAR (Fatal Accident Rate)

It is used by the British chemical industry. FAR reports the number of fatalities based
on 1000 employees working their entire lifetime. The employees are assumed to work
a total of 50 years. Thus FAR is based on 108 working hours.

Number of fatalities x 108

FAR 
Total hours worked by all emplyees during period covered

Fatality rate
Fatality rate or deaths per person per year is independent of the number of hours
actually worked. It is useful for calculations on the general population, where the
number of exposed hours is poorly defined.

Number of fatalities per year

Fatality rate 
Total number of people in applicable population

FAR can be converted to fatality rate (or vice versa) if the number of exposed hours is
known.

Example:
A process has reported FAR of 2. If an employee works a standard 8-h shift 300 days per
year, the deaths per person per year is

h day death
Fatality rate  8 x 300 x 2 8
 4.8 x 10 5 death per person per year
day year 10 h

Accident Statistics for Selected Industries

OSHA Fatality FAR
Industry incident (UK)
rate
2007 2000 1987-90
Agriculture 6.1 24.1 3.7
Chemical and allied 3.3 2.5 1.2
Coal mining 4.7 50 7.3
Construction 5.4 10 5.0
Vehicle manufacturing 9.3 1.3 0.6
All manufacturing 5.6 3.3 1.2

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 Fatality Statistics for Common Nonindustrial Activities
Activity FAR, Fatality rate,
deaths/108 hour death/person/year
Voluntary activity
Staying at home 3
Travelling by
Car 57 17x10 – 5
Bicycle 96
Air 240
Motorcycle 660
Smoking 4 x 10 – 5
Involuntary activity
Struck by lightening (UK) 1 x 10 – 7
Fire (UK) 150 x 10 – 7
Run over by vehicle (UK) 600 x 10 – 7

The risk resulting from multiple exposures are additive.

Engineers must make every effort to minimize risks within the economic constrains of
the process.

The general public has great difficulty with the concept of acceptable risk. The major
objection is due to the involuntary nature of acceptable risk. Chemical plant designers
who specify the acceptable risk are assuming that these risks are satisfactory to
civilians living near the plant. Frequently these civilians are not aware that there is any
risk at all.

1.4 The nature of the accident process

Chemical plant accidents follow typical pattern. Fires are the most common, followed
by explosion and toxic release. With respect to fatalities, the order reverses.

Types of loss for large hydrocarbon-chemical plant accidents

(Based on data from the 100 largest losses, 1972–2001)

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 Three Types of Chemical Plant Accidents
Type of Probability Potential for Potential for
accident of occurrence fatalities economic loss
Fire High Low Intermediate
Explosion Intermediate Intermediate High
Toxic release Low High Low

Sources of fire hazards:

 hot surfaces
 combustible and flammable liquids
 heat utilization equipment
 heat transfer equipment
 lighting
 ovens and furnaces (process flames)
 dehydrators and dryers
 quench tanks
 reactors (exothermic reactions)
 welding and cutting (maintenance flames)
 gas cylinders (potential bombs)
 static electricity (sparks)

Causes of fire and explosion hazards:

 Improper storage of flammable oils, greases, and fluids
 Smoking by employees
 Poor housekeeping
 Defective heating equipment, electrical equipment and wiring
 Explosive gas leakage
 Ignition of gases, vapours or combustible dust
 Inadequate electrical motors
 Sparking in electrical wires and equipment

The most damaging type of explosion is an unconfined vapour cloud explosion (VCE),
where a large cloud of volatile and flammable vapour is released and dispersed
through the plant site followed by ignition and explosion of the cloud.

By far the largest cause of loss in a chemical plant is due to mechanical failure usually
due to a problem with maintenance. Pumps, valves, and control equipment will fail if
not properly maintained. The second largest cause is operator error. For example,
valves are not opened or closed in the proper sequence or reactants are not charged to a
reactor in the correct order. Process upset can be caused by power failure or cooling
water failure.

Almost all accidents, except those caused by natural hazards, can be attributed to
human error. (For instance, mechanical failure could be due to human error as a result
of improper maintenance or inspection.)

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 Accidents, %
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Causes of losses in the largest hydrocarbon-chemical plant accidents (1972-2011)

Considering equipment failure, piping system failure represents the bulk of the
accidents, followed by reactors and storage tanks. The most complicated mechanical
components (pumps and compressors) are minimally responsible for large losses.
Details of a study are shown on the next figure.

Piping system 30

Reactors 26

Storage tanks 15

Uunknown 8

Instruments 5

Heat exchangers 4

Process towers 4

Pumps 4

Valves 2

Compressors 2

0 5 10 15 20 25 30 35

Number of accidents

Hardware associated with the largest hydrocarbon-chemical accidents

(Data from the 100 largest losses, 1972-2001)

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Most accidents follow a three-step sequence:
1.) Initiation (the event that starts the accident)
2.) Propagation (the event or events that maintain or expand the accident)
3.) Termination (the event or events that stop the accident or diminish it in size)

Example:
A worker walking across a high walkway in a process plant stumbles and falls toward the
edge. To prevent the fall, he grabs a nearby valve stem. Unfortunately, the valve stem shears
off and flammable liquid begins to spew out. A cloud of flammable vapour rapidly forms and
is ignited by a nearby truck. The explosion and fire quickly spread to nearby equipment. The
resulting fire lasts for 6 days until all flammable materials in the plant are consumed, and the
plant is completely destroyed. This disaster occurred in 1969 and led to a loss of $ 4.1
million.

In this example, the worker tripped to initiate the accident. The accident was propagated by
shearing off the valve and resulting explosion and growing fire. The event was terminated by
consumption of all flammable material. The example also demonstrates that even the simplest
accident can result in a major catastrophe.

Safety engineering involves eliminating the initiating step and replacing the
propagation step with termination events. The next table presents a few ways to
accomplish this.

Defeating the Accident Process

Step Desired Procedure
effect
Initiation Diminish Grounding and bonding
Inerting
Explosion proof electrical
Guard rails
Maintenance procedure
Hot work permits
Human factor design
Process design
Awareness of dangerous properties of a chemical

Propagation Diminish Emergency material transfer

Reduce inventory of flammable materials
Equipment spacing and layout
Non-flammable construction materials
Installation of check and emergency shutoff valves

Termination Increase Fire fighting equipment and procedures

Relief systems
Sprinkler systems
Installation of check and emergency shutoff valves

Accidents, once initiated, should not propagate and should be terminated as quickly as
possible.

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1.5 Inherent safety
An inherent safe plant relies on chemistry and physics to prevent accidents rather than
on control systems, interlocks, redundancy, and special operating procedure.
Inherently safer plants are tolerant of errors. A process that does not require complex
safety interlocks and elaborate procedures is simpler, easier to operate, and more
reliable. Smaller equipment, operated at less severe temperatures and pressures, has
lower capital and operating costs.

The safety of a process relies on multiple layer of protection. The first layer of
protection is the process design features. Subsequent layers include control systems,
interlocks, safety shutdown systems, protective systems, alarms, and emergency
response plans.

The following 4 words have recently been recommended to describe inherent safety:
(1) Minimize (intensification)
(2) Substitute (substitution)
(3) Moderate (attenuation and limitation of effects)
(4) Simplify (simplification and error tolerance)

Minimizing entails reducing the hazard by using smaller quantities of hazardous

substances in the reactors, distillation columns, storage vessels, and pipelines.

With substitution, safer materials are used in place of hazardous ones. When possible,
toxic or flammable solvents should be replaced by less hazardous ones (for examples,
water-based paints and adhesives, and aqueous or dry formulation for agricultural
chemicals).

Moderation is using a hazardous material under less hazardous conditions or less

hazardous form of a material includes
 diluting to a lower vapour pressure to reduce the release concentration,
 refrigerating to lower vapour pressure to reduce the release concentration,
 handling larger particle size solids to minimize dust,
 processing under less severe temperature or pressure conditions.

Simpler plants are friendlier than complex plants, because they provide fewer
opportunities for error and because they contain less equipment that can cause
problems. Simplification reduces the opportunities for errors and mis-operation. For
example,
 piping systems can be separated to prevent the domino effect,
 process steps and units can be placed in a logical order,
 fail-safe valves can be added, and
 the status of the process can be made visible and clear at all times.

Most accidents in chemical plants result in spills of toxic, flammable, and explosive
materials. Typical incidents include the rupture or break of a pipeline, a hole in a tank
or pipe, runaway reaction, or fire external to the vessel.

20
The studies of case histories provide valuable information to chemical engineers
involved with safety.

Inherent Safety Techniques

Type Typical techniques
Minimize Change from large batch reactor to a small continuous reactor
(intensification) Reduce storage inventory of hazardous intermediate chemicals
Improve control to reduce hold-up

Substitute Use mechanical pump seals vs. packing

(substitution) Use welded pipe vs. flanged
Use solvents that are less toxic
Use mechanical gauges vs. mercury
Use chemicals with higher flash points, boiling points, and other less
hazardous properties
Use water as a heat transfer fluid instead of hot oil

Moderate Use vacuum to reduce boiling point

(attenuation Reduce process temperatures and pressures
and limitation Refrigerate storage vessels
of effects) Dissolve hazardous materials in safe solvent
Operate at conditions where reactor runaway is not possible
Place control rooms away from operations
Separate pump rooms from other rooms
Acoustically insulate noisy lines and equipment
Barricade control rooms and tanks

Simplify Keep piping system neat and visually easy to follow

(simplification Design control panels that are easy to comprehend
and error Design plant for easy and safe maintenance
tolerance) Pick equipment that requires less maintenance
Pick equipment with low failure rate
Add fire- and explosion-resistant barricades
Separate systems and controls into blocks that are easy to
comprehend and understand
Label pipes for easy “walking the line”
Label pipes, vessels and controls to enhance understanding

1.6 Risk management and insurance

The science of risk management provides other avenues of protection beside a
technical solution to a risk. Four options of risk management are available to resolve a
concern. The four methods, in order of preference include:
1.) Risk avoidance
2.) Risk reduction
3.) Risk insurance
4.) Risk acceptance.

21
Risk insurance and risk acceptance are monetary measures that are dependent on the
financial options available to the companies’ management. They are based on the
company’s policy and preferences in the utilization of insurance measures and
available insurance policies in the market.

Risk avoidance involves eliminating the cause of the hazard. This is accomplished by
changes in the inherent risk features of a process or facility.

Risk reduction involves the provision of prevention measures or protection features

that will lessen the consequences of a particular incident. (E.g. firewalls, firewater
sprays, emergency shutdown systems, etc.)

Risk insurance is the method chosen when the possible losses are financially too great
to retain by risk acceptance and might in some cases be too expensive to prevent or
avoid. However, even the risk insurers (insurance companies) will want to satisfy
themselves that adequate precautions are being taken at facilities they are
underwriting. Thus they will look very carefully at the installations they are
underwriting. They will particularly examine risks they feel are above the industry
norm or have high loss histories within the industry.

Insurance engineers have become more sophisticated in their understanding of process

facilities and will want to physically tour and inspect locations for adequate risk
management practices, estimate loss potentials using incident computer modelling
programs, in addition to testing fixed protection measures. Where deficiencies are
noted the risk is elevated and the policies revised (e.g. coverage is dropped, premium
is raised, etc.)

As industries become ever-larger and more expensive, there may be cases where even
though an organization desires to obtain insurance, it may not be available in the
market. Therefore, even more “elaborate” risk reduction measures may have to be
employed.

Business interruption losses may also occur at a facility, as it is most likely a process
will have to shut down after an incident because it cannot function as intended.
Business interruption losses are generally 3 times the cost of the amount of physical
property damage.

22
2. FIRE AND EXPLOSION HAZARD
Fire and explosion hazards account for the major loss of life and property in the
chemical and petroleum industry. Organic solvents are the most common source of
fires and explosions in the chemical industry. Chemical and hydrocarbon plant losses
resulting from fires and explosions are substantial (annual $2.2 billion in USA).
Additional looses in life and business interruptions are also substantial.

To prevent accidents resulting from fires and explosions, engineers must be familiar
with
 the fire and explosion properties of materials,
 the nature of fire and explosion process, and
 procedures to reduce fire and explosion hazards.

2.1 The fire triangle

For a fire to occur there must be a fuel, an oxidizer, and an ignition source. In addition,
the combustion reaction must be self-sustaining. These elements are illustrated by the
fire triangle.

The fire triangle

Fire: when all sides are connected

No Fire: when any one side is missing

Methods of fire fighting thus depend on removing or shutting off the source of fuel,
excluding oxygen or removing heat (ignition source) from the fire faster than it
liberated.

A fourth condition is now recognized. Flames proceed

chemically as branched chain reactions through the
intermediary of free radicals, which are constantly being
formed and consumed. If the free radicals can be
removed and prevented from continuing the chain HEAT

reaction, the flame goes out. Various chemicals used in FUEL OXYGEN

dry powder and halogenated hydrocarbon extinguishers

capture free radicals and put off the fire this way. The CHAIN
fire triangle becomes a fire pyramid. REACTION

23
Fire, and its synonym combustion, is the rapid oxidation of an ignited fuel. It is an
exothermic chemical reaction that results from a runaway rate caused by temperature
or catalytic effects. The fuel can be in solid, liquid or vapour form, but vapour and
liquid fuels are easier to ignite. The combustion always occurs in the vapour phase;
liquids are volatilized and solids are decomposed into vapour before combustion. Fire
is among the most complex of transport processes.

Various fuels, oxidizers, and ignition sources common in the chemical industry are:
Fuels:
Liquids: petrol, acetone, ether, pentane
Solids: plastics, wood, dust, fibers, metal particles
Gases: acetylene, propane, CO, hydrogen
Oxidizers:
Gases: air, oxygen, fluorine, chlorine
Liquids: hydrogene peroxyde (H2O2), nitric acid (HNO3), perchloric acid
(HClO4)
Solids: metal peroxides (Na2O2, BaO2, ...), ammonium nitrite (NH4NO2)
Ignition sources:
Fire outbreak is a result of an ignition source such as heat (frictional
heat, hot equipment, exothermic reactions, hot engines, hot surface,
hot light bulb filament, overheating), sparks (generated when grinding
or welding), flames (process flames like in furnaces and maintenance
flames like during welding), electrical arcing, static electricity, sun-
on-glass effects, smoking and general carelessness.
IGNITION SOURCES ARE FREE!!!

Combustion products can be very toxic:

 soot, smoke – acid gases (HCl, SO2)
 CO2 – NOx
 CO (for incomplete combustion) – NH3
 HCN – acrolein CH2=CH–CHO
 phosgene COCl2 – metal fumes
 dioxins – furan

In the past, the sole method for controlling fires and explosions was elimination of or
reduction in ignition sources. Experience has shown that this is not robust enough —
the ignition energies for most flammable materials are too low and ignition sources are
too plentiful. As a result, current practice is to prevent fires and explosions by
continuing to eliminate ignition sources while focusing efforts strongly on preventing
flammable mixtures.

24
2.2 Classes of fire
Fires are classified based on the combustible material involved. This rationalizes the
choice of extinguishing media and devices.

USA EU Australia, Fuel Examples Extinguishing

Asia media
Ordinary wood, paper, water jet, foam
Class A Class A Class A combustibles PVC, textile,
rubber, rubbish
Flammable petrol, oil, dry powder, CO2,
Class B Class B
liquids benzene, ... foam,
Class B
Flammable natural gas, dry powder, CO2,
Class C Class C
gases propane, butane foam,
Un- Electrical short-circuits, CO2, dry powder
Class C Class E
classified equipment overloaded wire
Combustible Mg, Ti, Al, Na, dry powder
Class D Class D Class D
metals K, Fe, Ca, Li, U
Class K Class F Class F Cooking oil kitchen fires

Water has two different roles in extinguishing fires:

(1) Cooling the fire.
The latent heat of vaporization of water is very high, therefore water absorbs a
large amount of heat from the fire by turning into vapour. Without heat, the fuel
cannot keep the oxidizer burning to sustain the fire.

(2) Smothering the fire.

When water turns into vapour, it dilutes the oxygen in the air with water vapour
leaving the fire with insufficient amount of oxygen, and the fire dies out.
Combustion will stop when the air becomes "thin", that is when it contains less
than 15% oxygen.

Flammable liquids cannot be extinguished with water. If the liquid is lighter than water
and does not mix with it, the use of water may actually spread the fire by carrying the
liquid into surrounding areas, drains, cellars.

The major difference between fires and explosions is the rate of energy release. Fires
release energy slowly, whereas explosions release energy rapidly, typically on the
order of microseconds (μs). Fires can also result from explosions, and explosions can
result from fires.

2.3 Definitions
Fire: is a combustion process in which a substance rapidly combines with an oxidant
and releases energy. Fire involves the transport of atmospheric oxygen to the
combustion zone, its reaction with combustible material there, and the removal of
gaseous products of combustion. Part of the energy released is used to sustain the
reaction. That is fires are self-sustaining.

25
Ignition: Starting a fire. If the concentration of fuel is within the flammability limits
and the temperature of the mixture is high enough, the mixture will ignite.

Ignition temperature: The lowest temperature where ignition (production of flame)

occurs and burning will continue after the source of ignition or source of heat is
removed.

Autoignition: is when the ignition occurs without the presence of a spark or flame
.
Autoignition temperature (AIT): is the temperature where autoignition occurs.

Autoignition temperature varies with

 size of containments,
 material in contact, and
 concentration.

AIT is specific to a given composition. The measured value is apparatus related.

Examples of AIT:
benzene in quartz flask 571°C
iron flask 678°C

CS2 in 200 ml flask 120°C

1000 ml flask 110°C
10 L flask 96°C

pentane in air 1.5% 548°C

3.75% 502°C
7.65% 476°C

Flash point (FP): of a liquid is the lowest temperature at which it gives off enough
vapour to form an ignitable mixture with air near the surface of the liquid. It is a
measure of the ease of ignition of a liquid fuel. At the flash point, the vapour will
burn only briefly: the amount of vapour produced is inadequate to maintain
combustion. It is determined experimentally.

Fire point: is the lowest temperature at which a vapour above a liquid will continue to
burn ones ignited; the fire point temperature is higher than the flash point
temperature.

NFPA: National Fire Protection Association (USA)

Flammable liquids (NFPA): Liquids with a flash point < 38°C

(can burn at ambient temperature)

Combustible liquids (NFPA): Liquids with a flash point ≥ 38°C

(must be heated before they can burn)

OSHA and the EU uses the Globally Harmonized System (GHS) of Classification.
According to that system, the following classification is used:

26
Flammable liquids (OSHA, EU): Liquids with a flash point < 93°C

Flammable liquids are further subdivided into categories (OSHA, EU):

Category 1: liquids with flash point < 23°C and boiling point ≤ 35°C
(example: crude oil, diethyl ether, isopropylamine)
Category 2: liquids with flash point < 23°C and boiling point > 35°C
(example: petrol, lacquer thinner, ethanol, methanol, CS2, acetone,
benzene, isopropyl alcohol, cyclohexane)
Category 3: liquids with flash point ≥ 23°C and boiling point ≤ 60°C
(example: kerosene, aviation fuel)
Category 4: liquids with flash point > 60°C and boiling point ≤ 90°C
(example: diesel fuel, fuel oil)

Combustible dust: Any finely divided solid material that presents a fire or explosion
hazard when dispersed and ignited in air.

Flammability limits: Vapour-air mixtures will ignite and burn only over a well-
specified range of concentration. The minimum concentration of fuel in air
required for ignition at ambient temperature is the lower flammable limit
(LFL). Any fuel – air mixture below the LFL is too lean to burn. Conversely, the
concentration above which ignition will not occur is called the upper flammable
limit (UFL); the mixture is too rich. Both limits of flammability are published in
various handbooks for many hydrocarbons and chemicals in volume % fuel.

The flash point and flammability limits are not fundamental properties but are defined
only by a specific experimental apparatus and procedures used.

Most materials start to burn at 50% stoichiometric concentration.

Example:
Combustion of heptane C7H16 + 11O2 = 7CO2 + 8H2O

stoichiometric concentration of air: 11/0.21 = 52.38 mol air/mol heptane

at LEL with 50% stoichiometric concentration heptane is 0.5/52.38 ≈ 1 vol.%
For 1 vol.%, the vapour pressure is 1 kPa.
(temperature = – 5°C, flash point = – 4°C)

Lower explosion limit (LEL) and upper explosion limit (UEL) are used
interchangeably with LFL and UFL. Flammability limits are easily determined
experimentally.

27
 flammable

(50 – 100 μm)

flammable

The relationship between various flammability properties

Explosion: is a rapid expansion of gases and release of energy, resulting in a rapidly

moving pressure or shock wave. Explosion damage is caused by the shock wave.

Shock wave: is an abrupt pressure wave moving through a gas. A shock wave in open
air is followed by a strong wind; the combined shock wave and wind is called
blast wave. The pressure increase in the shock wave is so rapid that the process
is adiabatic.

Overpressure: is the pressure on an object as a result of an impacting shock wave.

A chemical explosion can be a deflagration or detonation.

Deflagration: is an explosion in which the reaction front moves at a speed less than
the speed of sound in the unreacted medium.

A deflagration is propagated at a low velocity (up to about 100 m/s in a solid)

and the burnt products stream in the opposite direction to that of the combustion
wave. The term low explosive is used for those that deflagrate. They are mainly
used as propellants and have low shattering power unless strongly confined.
Examples are gunpowder, gas mixture in the cylinder of an internal combustion
engine, fireworks. Overpressure < 0.5 bar.

The energy transfer from the reaction zone to the unreacted zone is accomplished
through ordinary transport processes of heat and mass transfer.

Detonation: It is an explosion in which the reaction front moves at a speed greater

than the speed of sound in the unreacted medium.

Detonations are observed in both conventional solid and liquid explosives, as

well as in reactive gases. The supersonic blast front (shock wave) propagates at a
high velocity in the range of 1-10 km/s. A detonation is a strong shock wave

28
 accompanied by a chemical reaction, which supplies the energy to maintain the
wave. The product of combustion streams in the same direction as the wave, and
high pressures are developed. The main cause of damage from detonations is due
to the shock wave. High overpressure up to 20 bar.

Detonating explosives are termed high explosives. Most high explosives have
shattering power even when unconfined.

In a gas, the shock wave compresses and heats the unburnt reactant in a way,
which causes it to react very quickly.

Many substances which deflagrate when ignites weakly will detonate under
sufficiently strong ignition. A deflagration wave may also accelerate into a
detonation wave.

Confined explosion: An explosion occurring within a vessel or a building. These are

the most common explosions usually resulting in injury to the building
inhabitants and extensive damage.

Unconfined explosion: occurs in the open. This type of explosion is usually the result
of a flammable gas spill. The gas is dispersed and mixed with air until it comes
into contact with an ignition source. They are rarer than confined explosions
because the explosive material is frequently diluted below the LFL by wind
dispersion. These explosions can be surprisingly violent and forceful. They have
mostly occurred in oil refineries and petrochemical works and in the storages and
transport of liquefied flammable gases.

Boiling-liquid expanding-vapour explosion (BLEVE): (pronounced ˈblɛviː

“blevee”) It occurs when a vessel containing a pressurized liquid above its
atmospheric boiling point ruptures. The subsequent BLEVE is the explosive
vaporization of a large fraction of the vessel contents; possibly followed by
combustion or explosion of the vaporized cloud if it is combustible.

Dust explosion: Most combustible solids in the form of fine dust are capable of
forming an explosive mixture when dispersed in air. The dust particle can be
either an unwanted by-product or the product itself. There are lower and upper
dust concentrations in air within which an explosion is possible and outside
which none is likely to occur. The explosion limits for a wide range of dusts are
between 50 g/m3 to 1000 g/m3. In appearance, such a dust cloud resembles a very
thick fog. In general, 70% of dusts are explosible.

Dust explosions generate pressures up to about 9 bar. Deflagrations are more

common than detonations. The pressure waves from dust deflagrations, however,
are powerful enough to destroy structures and kill or injure people.

Dust clouds are less easily ignited than most flammable vapours, a flame or hot
surface is generally needed to ignite them. Ignition temperatures for dust clouds
range between 300-700°C. Sulphur has an exceptionally low ignition temperature
of 190°C. 70% of dusts in the industry are explosive,

29
Factors affecting dust explosions:
– Particle size
– Chemical properties of the dust
– Moisture content of dust
– Cloud dispersion

The size of the dust particles is important in determining the force of the
explosion and whether one will occur. The most severe explosions occur with
particle diameters between 10-50 µm. Coarser dusts with particle diameters
above 200 µm present little or no explosion risk.

Examples of combustible dust:

light metals (Al, Mg), Fe, Zn, Mn
plastics: polystyrene, cellulose acetate, urea formaldehyde, resins
agricultural products: flour, sugar, cocoa, coffee, dust from grains, milk,
starch, wheat, corn, barley
coal, charcoal, rubber, wood dust, paper, cosmetics, soap, textiles, food,
pharmaceuticals, chemicals

Other, 7%
Inorganic, 4% Wood, 24%
Coal, 8%

Plastic, 14%

Food, 23%

Metal, 20%

Type of dust exploded

Other, 17.5% Mechanical

sparks, 30%

Self‐ignition,
6%

Welding, 5%

Hot surfaces, Static

6.5% electricity, 9%
Fires, 8%
Smolder spots, Friction, 9%
9%

Ignition sources of industrial dust explosions (OSHA, 2015)

30
Many of these sources are preventable with routine maintenance and fire safety
procedures. Keeping machinery properly maintained and cleaned will prevent it
from sparking during operation, which is the largest cause of explosions.

Other fixable problem areas include friction, static electricity, and electrical
equipment, but sometimes the risk from these ignition sources cannot be
completely prevented. When there is welding or hot surfaces, the ignition source
cannot be prevented, and in these cases a safe zone needs to be created and
maintained around the ignition source.

A fire or explosion in a workroom may stir up thick dust deposits, which have
settled on beams and other surfaces into a dust cloud, which can lead to
secondary explosions. Good housekeeping can eliminate the risk. The use of
compressed air in cleaning increases the probability of a dust explosion.

The type of plant and equipment in which dust cloud explosions have occurred:
– Size reduction equipment (milling, grinding, pulverizing and disintegrating
machines)
– Storage enclosures (silos, bins, hoppers)
– Pneumatic conveying systems
– Heating equipment (kilns, pneumatic dryers, rotary drum dryers, spray
dryers, fluidized bed dryers)
– Air-Material separators (screens, classifiers, bag filters, cyclones, settling
chambers, dust collectors)
– conveyors and elevators of various types

Protective measures:
– Making the equipment strong enough to withstand dust explosion,
– Placing the equipment out of doors or on the roof of a building,
– Use of explosion relief panels (they rupture above a certain pressure),
– Adding moisture to solids to reduce explosivity,
– Good housekeeping,
– Using of explosion suppression systems:
A fast acting pressure sensitive element detects the initial pressure rise and
transmits an electrical signal to 1 or more suppressors. The suppressor
contains a cartridge filled with compressed and liquefied CO2 or dry
powder. This is released by a detonator. Sufficient inert gas must be
released from the suppressor to dilute the O2 in the dust below the minimum
explosive concentration.
– Minimizing the fugitive explosive dust and preventing it from escaping
process equipment and ventilation systems,
– Installing dust collection systems,
– Using cleaning methods that do not generate dust clouds near ignition
sources. Avoiding compressed air cleaning method.

31
2.4 Flammability characteristics of liquids and vapours
Flash Points and Explosive Limits of Common Industrial Liquids
Explosive Limits, vol.%
Liquid Flash point, °C
Lower Upper
Acetone – 18 2.6 12.8
Benzene – 11 1.5 8.0*
Ethyl acetate –4 2.2 11.15*
Ethyl alcohol 13 3.5 19*
Ethyl ether – 45 1.0 50*
Hexane – 26 1.2 7.5
Kerosene 40 0.7 5*
Methanol 11 6.0 36*
Toluene 4 1.3 7.0*
Xylene 17 1.0 6.0*
Petrol – 43 1.4 7.6
Diesel 63 0.3 10
* At elevated temperature

Flash point determination of liquids

The flash point temperature is one of the major quantities used to determine the fire
and explosion hazards of liquids.

The flash point increases with increasing pressure.

There are several different experimental methods used to determine flash points. Each
method produces a somewhat different value. The open-cup flash point is a few
degrees higher than the closed-cup flash point.

Open-cup flashpoint determination: The liquid to be tested is placed in the open cup.
The liquid temperature is measured with a thermometer while a Bunsen burner is used
to heat the liquid. A small flame is lit at the end of a movable wand. During heating,
the wand is slowly moved back and forth over the open liquid surface. When a
temperature is reached at which the liquid is volatile enough to produce a flammable
vapour, a momentary flashing flame occurs. The temperature at which this occurs first
is called the flash point temperature.

32
 Cleveland open-cup flash point testing apparatus

Flammable liquids in the form of a dense mist or aerosol may be ignited easily at
temperatures below the liquid flash point. In combustion, mists made up of small
droplets < 10 μm behave like vapour whereas those with droplet diameters > 40 μm
propagate combustion in similar way to flammable dust clouds.
Flash point calculation for pure liquids
The flash point temperature for pure materials can be estimated with accuracy < 1%
from the boiling point (Tbp) of the liquid:

2
 c   c / Tbp
b   e
 Tbp 
 a   
 
T fp
 c / Tbp 2
1 e

where Tfp = flash point temperature, K

Tbp = boiling point temperature, K
a, b, c = constants

33
 Constants Used for Predicting the Flash Point
Chemical group a b c
Hydrocarbons 225.1 537.6 2217
Alcohols 230.8 390.5 1780
Amines 222.4 416.6 1900
Acids 323.2 600.1 2970
Ether 275.9 700.0 2879
Sulfurs 238.0 577.9 2297
Esters 260.8 449.2 2217
Ketones 260.5 296.0 1908
Halogens 262.1 414.0 2154
Aldehydes 264.5 293.0 1970
Phosphorous-containing 201.7 416.1 1666
Nitrogen-containing 185.7 432.0 1645
Petroleum fractions 237.9 334.4 1807

Flash point of multicomponent mixtures

Flash point can be estimated for multicomponent mixtures if only one component is
flammable and if the flash point of the flammable component is known.

The flash point is estimated by determining the temperature at which the vapour
pressure of the flammable component in the mixture is equal to the pure component
vapour pressure at its flash point.

The flash point of multicomponent mixtures with more than one flammable
component should be determined experimentally.
Flammability limits for gases and vapours
Flammability limits for vapours are determined experimentally in a closed vessel
apparatus (see under 2.13.3). Vapour-air mixtures of known concentration are added
and then ignited. The maximum explosion pressure is measured. The test is repeated
with different concentrations to establish the range of flammability for the specific gas.
Flammability limits for vapour mixtures
The flammability limits of mixtures can be estimated from the data for individual
combustible components using the Le Chatelier’s mixing rule:

yi
 LFLi
 1

where yi = mole fraction of combustible species i on a combustible basis

LFLi = lower flammable limit for component i, vol.%

A similar relationship can be used to estimate the UFL for a gas mixture.

34
If the concentration of a mixture of combustible gases is known, the LFL and the UFL
for the mixture can be approximated from:
1
LFLmix  n

yi
i 1
LFLi
and Le Chatelier equations
1
UFLmix  n
yi
 UFLi
i 1

where LFLmix = LFL for the mixture

UFLmix = UFL for the mixture
yi = mole fraction of component i on a combustible basis
n = number of combustible components

The LFL does not change significantly with pressure.

Above equations give reasonably good LFL and UFL values for hydrocarbon gases
and mixtures of H2, CO, and CH4. They give poor results for other gas mixtures.

It is required that flammability limit data at the same temperature and pressure used in
the le Chatelier equations. Flammability data reported in the literature may be from
disparate sources, with wide variability in the data. Combining data from disparate
sources may cause unsatisfactory results, which may be not obvious to user.

LFL can be estimated from the flash point:

Vapour pressure at flash po int

LFL 
760 mmHg

Flammability limit dependence on temperature

In general, the flammability range increases with temperature. The flammability limit
can be approximated at elevated temperatures as:

 0.75 (T  25) 
LFLT  LFL 25 1  
 H c 

 0.75 (T  25) 
UFLT  UFL 25 1  
 H c 

where T = temperature, °C
ΔHc= net heat of combustion, kcal/mol at 25°C

35
LEL, %

, °C

Effect of temperature on lower limits of flammability

Flammability limit dependence on pressure

Pressure has little effect on the LFL. The UFL increases significantly as the pressure is
increased. The following empirical equation has been developed:

UFL p  UFL  20.6 (log p  1)

where p = absolute pressure, MPa

UFL = upper flammable limit at 1 atm

Estimating flammability limits

For some situations it may be necessary to estimate the flammability limits without
experimental data. For many hydrocarbon vapours, the LFL and UFL are function of
the stoichiometric concentration (cst) of fuel:

LFL = 0.55 cst

UFL = 3.50 cst

where cst = concentration of fuel, vol.%

The stoichiometric concentration for most organic compounds is determined using the
general combustion equation:

CmHxOy + zO2 → mCO2 + (x/2) H2O

36
 x y
 zm   , mol O 2 /mol fuel
4 2

moles of fuel 100

cst  x 100 
moles of fuel  moles of air  moles of air 
1  
 moles of fuel 

100 100
 cst  
1  moles of O 2  z
1   1
0.21  moles of fuel  0.21

Substituting this result:

0.55 0.55 (100)

LFL  0.55 cst  100 
1 
z 1  4.76 m  1.19 x  2.38 y
0.21

3.50 3.50 (100)

UFL  3.5 cst  100 
z 1  4.76 m  1.19 x  2.38 y
1 
0.21

Another method correlates the flammability limits as a function of the heat of

combustion of the fuel:

 3.42
LFL   0.569 H c  0.05380 H c2  1.80
H c

This equation applies only in the UFL

UFL  6.30 H c  0.569 H c2  23.5
range of 4.9-2.3 vol.%

where ΔHc = heat of combustion of fuel, MJ/mol

1 kcal/mol = 4.184 kJ/mol

Above equations give good fit for organic materials containing C, H, O, N, and S.

Estimating flammability limits with above equations is not accurate; should only be
used for quick initial estimate, and should not replace accurate experimental data.

37
 Flammability limits in pure oxygen in vol.%
Compound Lower Upper
Hydrogen 4.0 94
Carbon monoxide 15.5 94
Ammonia 15.0 94
Methane CH4 5.1 61
Ethane C2H6 3.0 66
Ethylene C2H4 3.0 80
Propylene C3H6 2.1 53
Cyclopropane C3H6 2.5 60
Diethyl ether C4H10O 2.0 82
Divinil ether C4H6O 1.8 85

2.5 Limiting oxygen concentration and inerting

Oxygen is the key ingredient for combustion and there is a minimum oxygen
concentration required to propagate a flame. Explosions and fires can be prevented by
reducing the oxygen concentration regardless of the concentration of the fuel. This is
the concept for a common procedure called inerting.

Below the limiting oxygen concentration (LOC) the reaction cannot generate enough
energy to heat the entire mixture of gases (including the inert gases) to the extent
required for the self-propagation of the flame. The unit of LOC is % of moles of O2 in
total mole.

LOC has been called the minimum oxygen concentration (MOC), the maximum safe
oxygen concentration (MSOC), and other names depending on the literature.

Limiting Oxygen Concentrations (in vol.% O2 above which combustion can occur)
Gas or vapor N2/Air CO2/Air Gas or vapor N2/Air CO2/Air
Methane 12 14.5 Natural gas 12 14.5
Ethane 11 13.5 Methyl chloroform 14 –
Propane 11.5 14.5 Trichloroethylene 9 (100°C) –
n-Butane 12 15 Acetone 11.5 14
Ethylene 10 11.5 CS2 5 7
Propylene 11.5 14 CO 5.5 5.5
Benzene 11.4 14 Ethyl ether 10.5 13
Toluene 9.5 – H2 5 5.2
Styrene 9.0 – H 2S 7.5 11.5
Petrol 12 15 Methanol 10 12
Kerosene 10 (150°C) 13 (150°C) Ethanol 10.5 13

If experimental data are not available, the LOC is estimated using the stoichiometry of
the combustion reaction and the LFL. This procedure works for many hydrocarbons.

38
2.6 Flammability diagram
A general way to present the flammability of gas or vapour is by the triangular
diagram. Concentrations of fuel, oxygen, and inert material (in vol. % or mol %) are
plotted on the sides of the triangle. Each apex of the triangle represents the pure
material (100%).

Point A represents a mixture of 60% CH4, 20% O2, and 20% N2.

The air line represents all possible combinations of fuel plus air. The air line intersects
the N2 axis at 79% N2 (and 21% O2), which is the composition of pure air.

The stoichiometric line represents all stoichiometric combinations of fuel + O2.

The combustion reaction can be written in the form of

Fuel + z O2 → Combustion products

The intersection of the stoichiometric line with the O2 axis is given by: 100 
z 

1 z 
The stoichiometric line is drawn from this point to the pure N2 apex.

CH4 (fuel)

LOC

UFL in pure O2
A
•

Flammability UFL
zone

•
LFL in pure O2
O2
• N2 (inert)

LFL
Flammability diagram for methane

39
Any gas mixture containing oxygen below the LOC is not flammable.

The lower flammability limit is fixed regardless of the O2 and N2 concentrations

(approximately 5% CH4), but the upper flammability limit varies greatly according to
the O2 – N2 concentration.

The lower boundary of the flammability zone is mostly horizontal and can be
approximated by the LFL.

The shape and size of the flammability zone on a flammability diagram depends on:
– type of fuel
– temperature
– pressure
– inert species present

Thus, the flammability limits and the LOC also change with these parameters.

For safety, ¼ of the lower flammability concentration of oxygen should not be

exceeded.

Note that the lines defining the flammability zone are not exactly straight. The upper
boundary expands in size.

Approximating the flammability zone:

(given the flammability limits in air and the LOC)
1.) Draw the air line.
2.) Draw the stoichiometric line.
3.) Locate the LOC on the oxygen axis and draw a line parallel to the fuel axis.
Mark the intersection.
4.) Locate LFL and UFL on the air line.
5.) From the intersection, draw a horizontal line parallel with the nitrogen axis.
This line will locate LFL in pure O2.
6.) From the intersection, connect UFL point in air.
7.) Extend this line to the oxygen axis noting that this gives only a conservative
estimate of the upper flammability zone.

2.7 Ignition energy

The minimum ignition energy (MIE) is the minimum energy input required to
initiate combustion.

MIE depends on
– the specific chemical or mixture (it is higher for dusts than that of combustible
gases)
– concentration (an increase in N2 concentration increases MIE)
– pressure (decreases with increasing pressure)
– temperature

Many hydrocarbons have MIEs of about 0.25 mJ. This is low compared with sources
of ignition. A person walking across a carpeted floor can develop a potential difference

40
large enough for a 40 mJ discharge. Humans generally only sense discharges of 0.6 mJ
or more, which means that discharges we cannot detect may carry enough energy to
ignite a flammable mixture. Ordinary spark plug has a discharge energy of 25 mJ.
Electrostatic discharges, as a result of fluid flow, also have energy levels exceeding the
MIE of flammable materials and can provide an ignition source.

MIE for a mist is the same as that of the vapour of the material.

Minimum Ignition Energies

DUSTS MIE, mJ VAPOURS MIE, mJ
Aluminium 50 Acetone 1
Cellulose 35 Acetylene 0.02
Corn flour 20 Benzene 0.2
Corn starch 30-60 Carbon disulfide (CS2) 0.01
Coal 40 Ethylene 0.07
Cocoa 100 Heptane 0.2
Epoxy resin < 10 Hexane < 0.3
Grain dust 30 Hydrogen 0.01
Milk powder 50 Isopropyl alcohol 0.65
Paper dust 20-30 Methane, Ethane 0.25
Soap 60-120 Propane, Butane 0.25
Sugar 30 Methanol 0.14
Sulphur 15 Petrol 0.8
Wood flour 30-40 Toluene 0.2

2.8 Autoignition
The autoignition temperature (AIT) of vapour is the temperature at which the
vapour ignites spontaneously from the energy of the environment.

AIT is a function of:

– the concentration of vapour (rich or lean mixtures have higher AITs)
– volume of vapour (large system volumes decrease AIT)
– pressure of the system (an increase in pressure decreases AITs)
– oxygen concentration (increases in O2 concentration decreases AITs)
– presence of catalytic material
– flow conditions
– the size of the containment

It is essential to determine experimentally AITs at conditions as close as possible to

process conditions.

41
Some Autoignition Temperatures
Material AIT, °C
Acetone 465
Acetylene 305
Benzene 560
Butane 405
Charcoal 349
Diesel 210
Ethane 515
Ethanol 365
Fuel oils 210-260
Kerosene 295
Natural gas, methane 580
Paper 450
Petrol 246-280
Petroleum 400
Propane 470
Wood 300

Minimum Autoignition temperatures

42
2.9 Auto-oxidation
Auto-oxidation is the process of slow oxidation with accompanying evolution of heat,
sometimes leading to autoignition if the energy is not removed from the system.
Liquids with relatively low volatility are particularly susceptible to this problem.
Liquids with high volatility are less susceptible to autoignition because they self-cool
as a result of evaporation.

Many fires are initiated as a result of auto-oxidation, referred to as spontaneous

combustion. Some example: oils on a rug in a warm storage area, insulation on a steam
pipe saturated with certain polymers, filter aid saturated with certain polymers, etc.

2.10 Adiabatic compression

An additional means of ignition is adiabatic compression. (For example, petrol and air
in an automobile cylinder will ignite if the vapours are compressed to an adiabatic
temperature that exceeds the AIT. This is the cause of preignition knock in engines
that are run too hot and too lean. It is also the reason some overheated engines
continue to run after the ignition is turned off.)

Several large accidents have been caused by flammable vapours being sucked into the
intake of air compressors; subsequent compression resulted in autoignition.

The adiabatic temperature increase for an ideal gas is computed from the
thermodynamic adiabatic compression equation:
 1
T final  p final  
  
Tinitial  pinitial 

where Tfinal and Tinitial = final and initial absolute temperatures, K

pfinal and pinitial = final and initial absolute pressures, Pa
γ = cp/cv = 1.4 for air

2.11 Ignition sources

The sources of ignition are numerous, consequently it is impossible to identify and
eliminate them all. The elimination of ignition sources with the greatest probability of
occurrence should be given the greatest attention. Combination of sources must also be
investigated. The goal is to eliminate or minimize ignition sources because the
probability of fire or explosion increases rapidly as the number of ignition sources
increase. Increasing plant size increases significantly the potential ignition sources.

43
 Ignition Sources of over 25000 Major Fires (USA, 1974)
Ignition sources %
Electrical (wiring of motors) 23
Smoking 18
Friction (bearings or broken parts) 10
Overheated materials (abnormally high temperatures) 8
Hot surfaces (heat from boilers, lamps, etc.) 7
Burner flames (improper use of torches, etc.) 7
Combustion sparks 5
Spontaneous ignition (rubbish etc.) 4
Cutting and welding (sparks, arcs, heat, etc.) 4
Exposure (fire jumping into new area) 3
Maliciously set fires 3
Mechanical sparks (grinders, crushers, etc.) 2
Molten substances (hot spills) 2
Chemical action (process not in control) 1
Static sparks 1
Lightning 1
Miscellaneous 1

2.12 Sprays and mists

Static electricity is generated when mists or sprays pass through orifices. A charge
may accumulate and discharge in a spark. If flammable vapours are present, a fire or
explosion will occur.

Mists and sprays also affect the flammability limits. With drop diameters < 0.01 mm
(10 μm), the LFL is virtually the same as the substance in vapour form. This is true
even at low temperatures where the liquid is non-volatile and no vapour is present.
Mists of this type are formed by condensation.

For mechanically formed mists with drop diameters between 0.01-0.2 mm (10-200
μm) the LFL decreases as the drop diameter increases. With large drop diameters, the
LFL can be less than 1/10 of the normal LFL.

When sprays have drop diameters between 0.6-1.5 mm, flame propagation is
impossible. However, the presence of small drops and/or disturbances that shatter the
large drops may create a hazardous situation.

44
2.13 Explosions
Explosion behaviour depends on a large number of parameters:
– ambient temperature
– ambient pressure
– composition of explosive material
– physical properties of explosive material
– nature of ignition source: type, energy, duration
– geometry of surroundings: confined or unconfined
– amount of combustible material
– turbulence of combustible material
– time before ignition
– rate at which combustible material is released

Explosive behaviour is difficult to characterize and still not completely understood.

Practicing engineers, therefore, should use extrapolated results cautiously and provide
a suitable margin of safety in all design.

An explosion results from the rapid release of energy. The energy release must be
sudden enough to cause a local accumulation of energy at the site of explosion. This
energy is then dissipated by a variety of mechanism, including formation of pressure
wave, projectiles, thermal radiation, and acoustic energy. The damage from an
explosion is caused by the dissipating energy.

If the explosion occurs in a gas, the energy causes the gas to expand rapidly, forcing
back the surrounding gas, and initiating a pressure wave that moves rapidly outward
from the blast source. The pressure wave contains energy, which results in damage to
the surrounding. For chemical plants, much of the damage from explosion is due to
this pressure wave. Thus, in order to understand explosion impacts, we must
understand the dynamic of the pressure wave.

A pressure wave propagating in air is called a blast wave, because the pressure wave
is followed by a strong wind. A shock wave or shock front results if the pressure
front has an abrupt pressure change. A shock wave is expected from highly explosive
materials, such as TNT, but it can also occur from the sudden rupture of a pressure
vessel. The maximum pressure over ambient pressure is called peak overpressure.

TNT: trinitrotoluene C6H2(NO2)3CH3

2.13.1 Types of explosions

Explosions may be classed as:
– chemical explosions,
– physical explosions,
– mechanical explosions,
– electrical explosions, and
– nuclear explosions.

45
Chemical explosions
They are sometimes referred to as thermal explosions.
It may involve:
 the decomposition of an unstable compound or explosive (which may be a
mixture or a single compound), or
 the explosion of a mixture of air and some fuels (as in the internal combustion
engine). The fuel may be a gas or vapour, or a cloud of small droplets, or a
dust cloud.

Chemical explosives are classified into 2 groups:

 those, which are legally classified as explosives,
 other chemical compounds (a, b, d, and d cases).

(a) Spontaneous explosions of chemicals not recognised as explosives

Some unstable compound explodes spontaneously without the involvement of
atmospheric oxygen or some other chemical during storage, transport, or use. This
category includes a large number of compounds most of which are found in
laboratories, but a number of them are intermediates or by-products.

 Some compounds are stable at low pressure but liable to explode at high pressure.
 Others may decompose spontaneously under normal conditions at a very low rate.
When present in bulk, the heat generated by this slow decomposition is unable to
escape and raises the temperature of the material in the center to a point where the
speed of decomposition accelerates to an explosion (e.g. NH4NO3). The
decomposition of some compounds is promoted by catalysts (e.g. acids,
hydrocarbons, oils, organic compounds).
 Some may be exploded by a powerful impact (e.g. dinitro-compounds, organic
peroxides).

Examples:
acetylene (used for welding and cutting),
NH4NO3 (major component of many blasting explosives and many fertilizers),
ethers (form explosive peroxides when left in contacts with air and light),
H2O2 (reacts violently with many organic compounds),
nitroparaffins (paint and lacquer solvents), …

(b) Chemicals that react violently or explosively with water

 Some liberate flammable gases, which instantly burn or explode (e.g. Na, K, Al-
triethyl),
 Some liberate flammable gases, which may burn or explode later (e.g. CaC2),
 Others react with great evolution of heat, which may cause the mixture to boil.

Examples:
materials, which liberate H2: Ca, Li, Na, K, CaH2, LiH
materials, which liberate hydrocarbon: Al(C2H5)3, Al(C2H5)2Cl → form ethane
materials, which liberate O2: F2, Na2O2
materials, which generate steam: CaO (quicklime), activated alumina, activated
silica, NaOH, KOH

46
(c) Explosives in mixtures of chemicals not recognised as explosives
Many chemicals, which are not themselves explosives are liable when mixed with
some other chemicals with which they can react.

Examples:
rocket fuels: H2 + Cl2; liquid O2 + oil, greases, flammable gases and liquids; Al
powder (as paint) + iron oxide (rust); …

(d) Explosions of flammable gas or vapour mixtures with air

Explosions of this type are frequently accompanied by fires. They may be subdivided
into confined explosions and unconfined vapour cloud explosions. Both confined and
unconfined vapour cloud explosions usually originate in a leak of gas or vapour or
vapourising liquid into the atmosphere. While quite a small leak can cause explosion
inside buildings, an extremely large leak is needed in an unconfined vapour cloud
explosion out of doors.

Some of the properties of flammable gases and volatile liquids that affect their
behaviour in explosion:
 density, relative to air
lighter than air: tends to rise
nearly the same density as air: no rise or fall
higher density than air: forms layers near the ground and
accumulates in pits, basements, …
 flammability limits
 detonability limits – It lies within the flammability limits.
 ignition temperature
 gross calorific value.

The most dangerous gases and vapours are those with low ignition temperatures, wide
flammability limits, high calorific values and cannot be detected by smell.

The maximum pressure generated by the explosion of gas-air mixture in a confined

space lies between 6-9 atm when the mixture is at atmospheric pressure before the
explosion.

Physical explosions
Physical explosion results from the sudden formation of large quantities of vapour
from water or some other liquid coming into contact with some hotter material (e.g.
molten metal, hot metal, or hot oil).

Examples:
 water in moulds and ladles in foundry operations
 water coming into contact with hot oil of much higher boiling point
 in distillation and vacuum distillation columns at start up when pockets of
water lying in low parts of the columns come into contact with hot oil
circulating above them
 in storage tank which contains separate water and oil layers and heat
applied to only one of the layers and the contents are unstirred

47
To prevent physical explosion:
 not to allow water and oil at different temperatures to come into contact
 mixtures of water and oil should never be heated unless they are effectively
stirred
 refineries and other plants involving hot oils must drain water regularly,
especially during start up, from bottom of vessels, low points in pipe lines,
pumps and heat exchangers

The largest physical explosion recorded occurred during the Krakatoa eruption in 1883
when the sea poured into a submarine crater containing millions of tons of molten
lava. [Indonesian name of the island: Krakatau. The main explosion was heard 3500
km away in Perth, Australia and 4800 km away in Mauritius. The pressure wave went
around the globe 7 times in 5 days. Ash was propelled to a height of 80 km. Death toll
estimated 120 000. The explosion was equivalent to 200 Mt of TNT (840 PJ), about
13000 times the nuclear bomb dropped at Hiroshima. It ejected ~ 21 km3 of rock, ash,
and pumice.]

Most familiar example of physical explosion occurs when water is tipped into a large
pan of hot frying oil.

Mechanical explosions
Mechanical explosion results from the rupture of a vessel containing high-pressure
nonreactive gas such as boilers, pressure vessels, autoclaves and pressure cookers,
tires, gas cylinders, etc. Boiler explosions were quite common in the mid-nineteen
century.

There needs to be a transient pressure rise inside a pressure vessel to cause a

mechanical explosion.

Mechanical explosions may be caused by gradual overpressurization and over-

stressing of the container, by weakening of the container as a result of heat, corrosion
or mechanical damage, or by an internal explosion (chemical or physical) within the
container causing at least transient overpressurization. E.g.: the bursting of a
compressed air container will produce fragments, which will be accelerated to high
velocities and behave like missiles or bomb fragments.

Electrical explosions
Electrical explosion results from the sudden conversion of electrical energy into heat,
generally as a result of the breakdown of an insulator when the surrounding air
becomes ionized and conducting. An electrical explosion is nothing more than a very
large spark or series of sparks, typified in nature by lightning.

Nuclear explosions
Nuclear explosion is the most devastating and feared of all. There are two types,
depending on whether the energy is derived from the fission or fusion of atomic
nuclei. A fission explosion results when a quantity of fissile material, 235U or 239Pu, is
brought together suddenly into a critical condition. The energy yield may be
equivalent to the explosion of up to 100 000 t of TNT (100 kt) or even more. A fusion
explosion occurs when a light element such as tritium (3H) is heated to such a high

48
temperature that the rate of heat evolution through nuclear fusion exceeds the rate of
heat dissipation.
2.13.2 Detonation and deflagration
A chemical explosion can be a deflagration or detonation.

The damage effect from an explosion depends highly on whether the explosion results
from a detonation or a deflagration. The difference depends on whether the reaction
front propagates above or below the speed of sound in the unreacted gases. For ideal
gases, the speed of sound or sonic velocity is a function of temperature only and has a
value of 344 m/s at 20°C.

Detonation
In some combustion reactions, the reaction front is propagated by a strong pressure
wave, which compresses the unreacted mixture in front of the reaction front above its
autoignition temperature. This compression occurs rapidly, resulting in an abrupt
pressure change or shock wave in front of the reaction front. The reaction front and the
leading shock wave that propagates into the unreacted mixture is at or above the sonic
velocity.

The next figure shows the physical differences between a detonation and a deflagration
for a combustion reaction that occurs in the gas phase in the open. For a detonation,
the reaction front moves at a speed greater than the speed of sound. The shock front is
found a short distance in front of the reaction front. The reaction front provides the
energy for the shock front and continues to drive it at sonic or greater speeds.

Deflagration
For a deflagration, the reaction front propagates at a speed less than the speed of
sound. The pressure front moves at the speed of sound in the unreacted gas and moves
away from the reaction front. One way to conceptualize the resulting pressure front is
to consider the reaction front as producing a series of individual pressure fronts. The
pressure front moves away from the reaction front at the speed of sound and
accumulate together in a main pressure front. The main pressure front will continue to
grow in size as additional energy and pressure fronts are produced by the reaction
front.

The pressure front produced by detonations and deflagrations are markedly different.
A detonation produces a shock front, with an abrupt pressure rise, a maximum
pressure of greater than 10 atm, and a total duration of typically < 1 ms. The pressure
front resulting from a deflagration is characteristically wide (many millisecond in
duration), and with a maximum pressure typically 1-2 atm.

The behaviour of the reaction and the pressure fronts differ from those shown in the
next figure depending on local geometry constraining the fronts. Different fronts occur
if the fronts propagate in a closed vessel, a pipeline, or through a congested process
unit.

A deflagration can also evolve into a detonation. This is called a deflagration to

detonation transition (DDT). The transition is particularly common in pipes but
unlikely in vessels or open spaces.

49
DETONATION

15 Peak overpressure
Reaction Shock

Pressure, atm
front front
Shock front

Ambient pressure
0

Distance

DEFLAGRATION

8 Peak overpressure
Reaction Pressure
Pressure, atm

front front

Ambient pressure
0

Distance

2.13.3 Confined explosions

A confined explosion occurs in a confined space, such as a vessel or a building. The
two most common scenarios involve vapours and explosive dusts.

The nature of the explosion depends on several characteristics:

– the type of explosive material,
– flammability and explosive limits of the material,
– the rate of pressure rise after the flammable mixture is ignited, and
– the maximum pressure after ignition.

These characteristics are determined in laboratory.

50
 Test apparatus for acquiring vapour explosion data

Typical pressure vs. time data obtained from gas explosion apparatus

2.13.4 Blast damage resulting from overpressure

The explosion of dust or gas (either as a deflagration or as a detonation) results in a
reaction front moving outward from the ignition source preceded by a shock wave or
pressure front. After the combustible material is consumed, the reaction front
terminates, but the pressure wave continues its outward movement. A blast wave is
composed of the pressure wave and the subsequent wind. It is the blast wave that
causes most of the damage.

51
 Pressure

• • • •
•
to t1 t2 t3 t4 Time

Blast wave pressure at a fixed location

The shock duration is the period of greatest destruction to freestanding structures, so

its value is important for estimating damage.

For most of the underpressure period (t2 – t4) the blast wind reverses direction and
flows toward the explosion origin. The maximum underpressure is only a few kPa.
The underpressure for large explosions and nuclear explosions, however, can be quite
large, resulting in considerable damage.

The overpressure can be estimate by:

r
ze  Scaling law
mTNT  1 / 3
where ze = scaled distance, m/kg1/3
r = distance from the ground zero point of explosion, m
mTNT = equivalent mass of TNT, kg

The equivalent energy of TNT is about 1200 kcal/kg (4.5 MJ/kg)

52
 Correlation between scaled distance and explosion peak overpressure

po
ps 
pa

where ps = scaled overpressure, dimensionless

po = peak overpressure
pa = ambient pressure

The procedure for estimating the overpressure at any distance r resulting from the
explosion of a mass of material is as follows:
1.) Compute the energy of explosion using thermodynamic procedure
2.) Convert the energy to an equivalent amount of TNT
3.) Use the scaling law and the correlation of above figure to estimate the
overpressure
4.) Use the table to estimate the damage

53
Damage Estimates for Common Structures Based on Overpressure
Over- Damage
pressure,
kPa
0.15 Annoying noise (137 dB if of low frequency of 10-15 Hz)
0.2 Occasional breaking of large glass windows already under strain
0.3 Loud noise (143 dB), sonic boom, glass failure
0.7 Breakage of small windows under strain
1.0 Typical pressure for glass breakage
2.1 “Safe distance” (probability 0.95 of no serious damage below this value);
some damage to house ceilings; 10% of window glass broken
2.75 Limited minor structural damage
3.4-6.9 Large and small windows shatter
4.8 Minor damage to house structures
6.9 Partial demolition of houses
6.9-13.8 Corrugated asbestos shutters; corrugated steel or alumina panels
fastening fails followed by buckling; wood panels fastening fail, panels
blow in
9.0 Steel frame of clad building slightly distorted
13.8 Partial collapse of walls and roofs of houses
13.8-20.7 Concrete block walls, not reinforced, shatter
15.8 Lower limit of serious structural damage
17.2 50% destruction of brickwork of houses
20.7 Heavy machines (1.4 t) in industrial buildings suffer little damage; steel
frame buildings distorts and pull away from foundations
20.7-27.6 Frameless, self-framing steel panel buildings demolished; rupture of oil
storage tanks
27.6 Cladding of light industrial buildings ruptures
34.5 Wooden utility poles snap
34.5-48.2 Nearly complete destruction of houses
48.2 Loaded train wagons overturned
48.2-55.1 Brick panels (20-30 cm thick), not reinforced, fail by shearing
62.0 Loaded train boxcars completely demolished
68.9 Probable total destruction of buildings; heavy machine tools (3 t) moved
and badly damaged; very heavy machine tools (54 t) survive

54
 Impact of VCEs on People
Peak Equivalent Effect
overpressure, wind velocity,
kPa km/h
7 Knock personnel down
15 110
35 260 Rupture eardrums
70 470
100 Damage lungs
140 760
200 1100
240 Threshold fatalities
340 1500 50% fatalities
450 99% fatalities

2.13.5 TNT equivalency

TNT equivalency is a simple method for equating a known energy of a combustible
fuel to an equivalent mass of TNT. The assumption is that an exploding fuel mass
behaves like exploding TNT on an equivalent energy basis.

The equivalent mass of TNT is estimated as:

 m H c
mTNT 
ETNT

where mTNT = equivalent mass of TNT, kg

η = empirical explosion coefficient, dimensionless
m = mass of hydrocarbon, kg
ΔHc = energy of explosion of a flammable gas  heat of combustion, kJ/kg
ETNT = energy of explosion of TNT = 1120 kcal/kg = 4686 kJ/kg

For many materials, the heat of combustion and energy of explosion differ by less than
10%.

The explosion coefficient (explosion efficiency) η is one of the major problems in the
equivalency method. It varies between 1-10%. The explosion efficiency is empirical.

The method tends to overpredict the overpressure near the VCE and to underpredict it
at distances away from the VCE. The advantage of TNT equivalency method is that it
is easy to apply because the calculations are simple.

Calculation procedure:
1.) Determine the total quantity of material involved in the explosion.
2.) Estimate η explosion efficiency and calculate mTNT equivalent.
3.) Use the scaling law to estimate the peak overpressure.
4.) Use the table to estimate the damage.

55
The procedure can be applied in reverse to estimate the quantity of material involved
based on the damage estimates.

2.14 Missile damage

An explosion occurring in a confined vessel or structure can rupture the vessel or
structure, resulting in the projection of debris over a wide area. These debris, or
missiles, can cause appreciable injury to people and damage to structures and process
equipment.

Unconfined explosions can also create missiles by blast wave impact and subsequent
translation of structures.

Missiles are frequently a means by which an accident propagates through a plant

facility. A localized explosion in one part of the plant projects debris through the plant.
These debris strike storage tanks, process equipment, and pipelines, resulting in
secondary explosions.

2.15 Vapour cloud explosion (VCE)

The most dangerous and destructive explosions in the chemical process industries are
VCEs.

These explosions occur in a sequence of steps:

1.) Sudden release of a large quantity of flammable vapour (typically this
occurs when a vessel, containing a superheated or pressurized liquid,
ruptures)
2.) Dispersion of vapour through the plant site while mixing with air
3.) Ignition of the resulting vapour cloud

What happens to a vapour cloud?

– Cloud will spread from too rich, through flammable range to too lean.
– Edges start burn through deflagration (steady state combustion).
– Cloud will disperse through natural convection.
– Flame velocity will increase with containment and turbulence.
– If velocity is high enough cloud will detonate.
– If cloud is small enough with little confinement it cannot explode.

VCEs occur in oil refineries, petrochemical works and in the transportation of

liquefied flammable gases.

56
Types of materials, which have most commonly given rise to unconfined vapour cloud
explosion are:
 LPG
 light hydrocarbon gases in processes at a high pressure (>35 atm) and in large
quantity
 hydrocarbons containing 5-9 C atoms/molecule, which are contained as liquids
in vessels under moderate pressures and temperatures substantially above their
boiling points at atmospheric pressure (high-pressure polythene plants,
cyclohexane oxidation plants, etc)

VCEs have increased in number because of an increase in inventories of flammable

materials in process plants and because of operations at more severe conditions. Any
process containing quantities of liquefied gases, volatile superheated liquid or high-
pressure gases is considered a good candidate for a VCE (e.g. crude oil tanks fitted
with steam coils in the base, large pressurized LPG storage vessels, large road and rail
LPG tank cars, ethylene plants, high-pressure polythene plants, cyclohexane oxidation
plants, etc.).

Some of the parameters that affect VCE behaviour:

– quantity of material released
– fraction of material vaporized
– probability of ignition of the cloud (increases with the size of the vapour
cloud)
– distance travelled by the cloud before ignition
– time delay before ignition of cloud
– probability of explosion rather than fire (vapour cloud fires are more common
than explosions)
– existence of a threshold quantity of material
– efficiency of explosion (usually small, ~2% of the combustion energy is
converted into blast wave)
– location of ignition source with respect to release (ignition of the cloud at a
point remote from the release increases the impact of explosion)
– turbulent mixing of vapour (increases the impact of explosion)

From safety standpoint, the best approach is to prevent the release of material. A large
cloud of combustible material is dangerous and almost impossible to control, despite
any safety system installed to prevent ignition.

Methods to prevent VCEs include:

– keeping low inventories of volatile, flammable materials
– using process conditions that minimize flashing if a vessel or pipeline ruptured
– using analyzers to detect leaks at low concentrations
– installing automated block valves to shut systems down while the spill is in the
incipient stage of development
– generous spacing between hazardous plants.

57
2.16 Boiling liquid expanding vapour explosion (BLEVE)
A BLEVE occurs when a tank containing a liquid held above its atmospheric boiling
point ruptures, resulting in the explosive vaporization of a large fraction of the tank
contents.

The mechanism of the explosion

The vapour portion may rapidly leak from the ruptured vessel, lowering the pressure
inside the container. This sudden drop in pressure inside the container causes violent
boiling of the liquid, which rapidly liberates large amounts of vapour. The pressure of
this vapour can be extremely high, causing a significant wave of overpressure (an
explosion) which may completely destroy the storage vessel and project fragments
over the surrounding area.

The vessel can fail due to corrosion, pressure build-up, or external fire. The most
common type of BLEVE is caused by external fire.

When BLEVE is caused by an external fire near the storage vessel, the fire is heating
the contents of the tank and pressure builds up. While tanks are often designed to
withstand great pressure, constant heating can cause the metal to weaken and
eventually fail. The tank wall below liquid level is cooled by the boiling liquid. If the
tank is being heated in an area, where there is no liquid only vapour, it may rupture
faster without the liquid to absorb the heat. Gas containers are usually equipped with
relief valves that vent off excess pressure, but the tank can still fail if the pressure is
not released quickly enough.

If the substance involved is flammable, it is likely that the resulting cloud of the
substance will ignite after the BLEVE has occurred, forming a fireball and possibly a
fuel-air explosion, also termed a vapour cloud explosion (VCE). If the materials are
toxic, a large area will be contaminated.

A BLEVE can occur even with non-flammable substances such as water, liquid
nitrogen, liquid helium or other refrigerants or cryogens, and therefore is not
considered a type of chemical explosion. It is a type of mechanical explosion.
Liquefied petroleum gas (LPG), propane etc. storage and transport vessels (tankers)
are prone to BLEVE.
2.16.1 Flashing liquids
When a BLEVE occurs in a vessel, only a fraction of the liquid vaporizes. Flashing
occurs so rapidly that the process is assumed to be adiabatic. The excess energy
contained in the superheated liquid vaporizes the liquid and lowers the temperature to
the new boiling point.

58
The excess energy of the superheated liquid is:

Q = m cp (To – Tbp)

where Q= superheat, kJ
m= mass of original liquid, kg
cp = specific heat capacity of liquid, kJ/kg
To = temperature of liquid before depressurization, °C
Tbp= depressurized (atmospheric) boiling point of the liquid, °C

This energy vaporizes the liquid:

Q = mv ΔHv

where mv = mass of liquid vaporized

ΔHv= latent heat of vaporization of the liquid, kJ/kg

Q m c p (To  Tbp )
Therefore mv  
H v H v

The fraction of liquid vaporized is:

mv c p (To  Tbp )
fv  
m H v

This equation assumes constant physical properties over the temperature range of To to
Tbp. If physical properties are not constant:

m cp
dm  dT
H v

m  mv Tbp
dm cp
 m
  H v
dT
m To

m  mv c p (To  Tbp )
ln  
m H v

where c p = mean specific heat capacity, kJ/kgK

H v = mean latent heat of vaporization, kJ/kg

Solving for fraction vaporized we get:

  c p (To  Tbp ) 
f v  1  exp  
 H v 
59
3. DESIGNS TO PREVENT FIRES
AND EXPLOSIONS
A twofold strategy is used to limit the potential damage from fires and explosions:
(1) Prevent the initiation of the fire or explosion
(2) Minimize the damage after a fire or explosion has occurred.

For any fire or explosion to occur, the three conditions shown by the fire triangle must
be met:
(1) Combustible or explosive material must be present
(2) Oxygen must be present to support the combustion reaction
(3) A source of ignition must be available to initiate the reaction

If any of above three conditions is eliminated, fire or explosion cannot occur. This is
the basis for the following methods:
– Inerting
– Use of flammability diagram
– Controlling static electricity
– Ventilation
– Explosion-proof equipment and instruments

Damage resulting from fires and explosions is minimized by

– stopping fires and explosions as quickly as possible
– designing process equipment (and control centers) to withstand their effects

3.1 Inerting
Inerting is the process of adding an inert gas to a combustible mixture to reduce the
concentration of O2 below the limiting oxygen concentration (LOC). The inert gas is
usually N2 or CO2, although steam is sometimes used. For many gases, the LOC is
~10%, and for many dusts is ~ 8%.

Inerting begins with an initial purge of the vessel with inert gas to bring the O2
concentration down to 4% below the LOC; that is 6% O2 if the LOC is 10%.

After the empty vessel has been inerted, the flammable material is charged. The
inerting system has to maintain an inert atmosphere in the vapour space above the
liquid. The inerting system includes an automatic inert gas addition feature; the control
system has an analyzer to continuously monitor the O2 concentration.

There are several purging methods used to initially reduce the O2 concentration to the
low set point:
(1) Vacuum purging
(2) Pressure purging
(3) Combined pressure-vacuum purging
(4) vacuum and pressure purging with impure N2

60
3.1.1 Vacuum purging
Vacuum purging is the most common inerting procedure for vessels and reactors, but
not for storage vessels, because they cannot withstand vacuum by design.

The steps in vacuum purging process are:

(1) drawing a vacuum on the vessel to a desired level
(2) relieving the vacuum with the inert gas to atmospheric pressure
(3) repeating steps (1) and (2) until the desired O2 concentration is reached
Pressure

yo y1 y2
pH

yo y1
pL

O2 conc. is const. No. of mol of O2 is const.

End of 1st End of 2nd Time

vacuum purge vacuum purge

Vacuum purge cycles

Determine the number of cycles required to achieve the desired O2 concentration

Assuming ideal gas behaviour, the total moles at each pressure are:

PH V PL V
nH  and nL 
RT RT
where nH = total moles in atmospheric state
nL = total moles in vacuum state
PH = high pressure (atmospheric)
PL = low pressure (vacuum)

Number of moles of O2 from Dalton’s law:

( nO2 )1H  yo nH yo = initial oxygen concentration

1H = first atmospheric state
1L = first vacuum state
( nO2 )1L  yo nL

61
When the vacuum is relieved with purge N2, the number of moles of O2 are the same
as in the vacuum state and the moles of N2 increase.

The new (lower) O2 concentration is:

( nO2 )1L
y1  where y1 = O2 conc. after the 1st purge
nH

( n O 2 )1 L nL
 y1   yo
nH nH
If the vacuum and inert relief is repeated, the concentration after the 2nd purge is:
2
( nO 2 ) 2 L n n 
y2   y1 L  y o  L 
nH nH  nH 

The total moles of N2 added for each cycle is constant.

For j cycles the total moles of N2 added is:

V
n N  j ( PH  PL )
2 j = number of cycles
RT

3.1.2 Pressure purging

Pressure purging is done by adding gas under pressure. After this added gas is diffused
through the vessel, it is vented to the atmosphere, usually down to atmospheric
pressure. More than one pressure cycle is usually necessary to reduce the O2
concentration to the desired level.

In this case, the vessel is initially at PL and is pressurized using a source of N2 at PH.
The objective is to determine the number of pressure cycles required to reach the
desired O2 concentration.

The relationship used for this purging process is identical to the final formula for the
vacuum purging process. The initial O2 concentration in the vessel yo is computed after
the vessel is pressurized (the 1st pressurized state).

One advantage of pressure purging vs. vacuum purging is the potential for cycle time
reduction. The pressurization process is much more rapid compared to the relatively
slow process of developing vacuum. Pressure purging, however, uses more inert gas.
Therefore, the best purging process is selected based on cost and performance.

62
 Pressure y1 y2
pH

yo y1 y2
pL

O2 conc. is const. No. of mol of O2 is const.

End of 1st End of 2nd Time

pressure purge pressure purge

Pressure purge cycles

3.1.3 Purging with impure nitrogen

Above equations developed apply for purging with pure N2 only. Many of the nitrogen
separation processes however provide N2 > 98% and not pure N2.

Assume the nitrogen contains O2 with a constant mole fraction of yO2. For a pressure
purging procedure the total moles of O2 present at the end of the first pressurization is
given by the moles initially present plus the moles included with the nitrogen. This
amount is:
PV V
nO  y o L  y O ( PH  PL )
2 2
RT RT

The total moles in the vessel at the end of the 1st pressurization are given as before:

PH V
nH 
RT

Thus the mole fraction of O2 at the end of the 1st cycle is:
nO PL  P 
y1  2
 yo  y O 1  L 
 PH 
2
ntotal PH

At the end of the jth pressure cycle:

PL  P 
y j  y j 1  y O 1  L 
 PH 
2
PH
63
and
j
P 
y j  yO   L  ( y o  y O )
 PH 
2 2

This equation is to be used for both pressure and vacuum purging in place of the last
formula given under vacuum purging.

3.2 Static electricity

Static electricity is an imbalance of electric charges within or on the surface of a
material. The charge remains until it is able to move away by means of an electric
current or electrical discharge.

A static electric charge is created whenever two different materials come into contact
and are separated, or when they are rubbed together and at least one of the surfaces has
a high resistance to electrical current (and is therefore an electrical insulator).

A common ignition source in chemical plants is sparks resulting from static charge
build-up and sudden discharge. It is by nature unpredictable and therefore difficult to
detect. Despite considerable efforts, serious explosions and fires caused by static
ignition continues to plague the chemical, petrochemical, plastics, pharmaceutical,
foodstuff, printing and paint industries.

Static electricity is always present in the industrial environment.

Common household examples that result in a build-up of static electric charge are
walking across a carpet, combing hair, removing a pullover etc. A common source of
static electricity in industry is the movement and transport of nonconductive liquids
or flammable substances in powder form.

A material is a conductor, when its resistance is < 104 Ω, and it is an insulator, when
its resistance is  1011 Ω.

There have been sudden occurrences of electrostatic disasters at plants that have
operated continuously for more than 10 years without an accident and in operations
that have been performed by hand by humans several thousand times without
accidents, so past history gives no guaranty for the future.

When liquids are filtered, sprayed, pumped, stirred/mixed, or flow through pipes,
discharge of liquid droplets and solid particles at high pressure, leaking steam that
contacts an ungrounded conductor; pneumatically conveying, grinding, blending or
sieving solids; movement of people or vehicles along insulating floors and the
movement of transmission belting or other forms of sheet materials over pulleys or
rollers, static electricity can be generated.

This type of “internal” static charge cannot be eliminated by bonding or grounding.

The static charges accumulate to develop large voltages. Subsequent grounding
produces large sparks.

64
For industrial operations where flammable vapours may be present, any charge
accumulation exceeding 0.1 mJ is considered dangerous. (The static build-up created
by walking across a carpet averages ~ 20 mJ and exceeds several thousand volts.)

Some accidents caused by static:

– Before 1960 in hospital operating theatres they used flammable mixtures of
anaesthetics and air (average 5 explosions a year in Great Brittan)
– Washing of oil tankers (sparks from clouds of charged water droplets formed during
tank cleaning using high-pressure water jets)
– Oil tanker: CO2 was discharged from a cylinder into a tank containing petrol to
create an inert atmosphere
– In-plants handling combustible powders and dusts in dryers and pneumatic
conveyors
– Pneumatic charging of combustible powder into large silos
– Resin powders were poured into stirred vessel containing xylene to dissolve them
– Moving belts of plastic films, fabrics, and paper passing over rollers

Some typical situations capable of producing static electricity

65
To prevent ignition by static, one must understand
(1) how charges accumulate on objects,
(2) how charges discharge by means of charge transfer, and
(3) how to estimate the resulting energy discharge in relation to the minimum
ignition energy (MIE) of explosive environment.
3.2.1 Charge accumulation
There are 4 charge accumulation processes that are relevant to dangerous electrostatic
discharges in a chemical plant:

(1) Contact and frictional charging (tribocharging)

When two materials, with one being a poor conductor, are brought into contact, a
charge separation occurs at the interface. This is known as the triboelectric effect. If
the 2 objects are then separated, some of the charges remain separated, giving the two
materials opposite but equal charges.

Examples: flow or pneumatic transport of powders/solids, pouring solids down chutes or

troughs, gears and belts transporting charges from one surface to another

(2) Double-layer charging

A double layer (also called an electrical double layer) is a structure that appears on the
surface of an object when it is exposed to a fluid. The object might be a solid particle,
a gas bubble, a liquid droplet, or a pipe wall. The double layer refers to two parallel
layers of charge surrounding the object.
– +
– +

metal

fluid
Charge separation occurs on a microscopic scale in a liquid at any interface
(solid-liquid, gas-liquid, or liquid-liquid). As the liquid flows, it carries a charge – +
and it leaves a charge opposite sign on the other surface (e.g. pipe wall). – +
– +
Example: flowing liquids, splash filling (the non-conducting fluids or solids free fall through
air picking up significant static charge), spraying

(3) Induction charging

This phenomenon is applicable only to materials that are electrically conductive. A
charged object brought close to an electrically neutral object causes a separation of
charge within the neutral object.

Example:
A person with insulated shoes may approach an overhead vessel that is
positively charged (previously filled with positively charged solids).
Electrons in the person’s body (head, shoulders, and arms) migrate toward
the positive charge of the vessel, thus accumulating an equal quantity of
positive charges on the opposite side of his body. This leaves the lower part
of his body positively charged by induction. When he touches a metal object,
there is a transfer of electrons, creating a spark.

66
 An isolated conductor is subject to an electric
field (man in insulated shoes). Charges of
different polarity are induced on opposite sides. If
an earthed electrode touches or approaches the
body then the charges closest to the electrode flow
away leaving the body with a net charge of
opposite sign.

Occurs by walking across carpets, asphalts,

plastic tiles etc.

Nonconductive shoes are a problem.

(4) Charging by transport

When charged liquid droplets or solid particles settle on an insulated object, the object
is charged. The transferred charge is a function of the object’s capacitance and of the
conductivities of the droplets, particles, and interface.

As electrostatic charge is generated by the means described above, it will either

accumulate or dissipate depending on the conductivity of the materials involved.

In practice, charge may accumulate on electrically insulated conductors, on insulating

surfaces, or on highly insulating liquids, powders or granules (e.g. plastic surfaces,
hydrocarbon liquids, polymeric powders, combustible dust clouds, and mists).

There can be no charge build up on the surfaces of conductive materials if they are
sufficiently conductive and grounded.

Fortunately, charge dissipation occurs even at relatively high resistances to earth.

Since the charging currents due to charge separation processes are very low (<10–6 A),
leakage of charge via resistances to earth of 106–108 Ω is sufficient to prevent
hazardous level of charge accumulation. However, plastic materials like polyethylene,
polypropylene, etc., or apolar liquids such as kerosene, hexane, etc. has resistances to
earth far above this order of magnitude.
3.2.2 Electrostatic discharges (ESD)
As accumulation of charges grows higher, the resulting electric field intensity in the air
may reach its limit value called the breakdown voltage of air of 3 MV/m (30 kV/cm),
or the charged surface may reach a maximum charge density of 2.7x10–5 C/m2. At this
limit, a discharge may occur to a ground or to an oppositely charged object when they
67
are close together. The total or only part of the energy stored in the charge
accumulation may be released forming a hot discharge channel that may ignite a given
flammable atmosphere.

(Breakdown voltage of an insulator is the minimum voltage that causes a portion of

an insulator to become electrically conductive.)

The energy released in the discharge and the minimum ignition energy (MIE) of the
flammable atmosphere determine whether ignition will occur or not.

A charged object can be discharged by six methods:

(1) Spark discharge
(2) Propagating brush discharge
(3) Conical pile discharge
(4) Brush discharge
(5) Lightening-like discharge
(6) Corona discharge

Common electrostatic discharges

(1) Spark discharge

It is a discharge between 2 conducting objects at different potential as soon as the
electrical field in the gap reaches the breakdown value of ~ 3 MV/m under normal
atmospheric conditions. The discharge continues until virtually all the charge has been
transferred. Energy transfer: up to 10 J (10,000 mJ)

68
In practice, one of these conductors (including personnel) reaches a high potential
since it is not connected to earth; the other conductor is normally at earth potential.
Because both objects are conductive, the electrons move to exit at a single point. This
is an energetic spark that can ignite a flammable dust, vapour or gas. Spark discharges
are responsible for the majority of industrial fires and explosions caused by static
electricity.

Typical examples of charge build up on isolated conductors:

 ungrounded metal fixtures and fittings
 human body insulated from earth by insulating shoes and/or insulating floor
 mobile and non-fixed items such as trolleys, metal drums gauging equipment, hand
tools
 metal funnel mounted on top of a pipe made from insulating material
 piece of metal pipe insulated from earth by non-conducting gaskets
 metal drum on a trolley with insulating tyres
 metal tool held by an operator wearing insulating gloves
 metal powder collected in a plastic bin
 conducting liquid filled into a drum with non-conducting internal coating

(2) Propagating brush discharge

Propagating brush discharge can occur when an insulating surface of up to 8 mm thick
(e.g. a teflon or glass lining of a grounded metal pipe or reactor) has become highly
polarised with electrostatic charge, that is positive charge on one face and negative
charge on the opposite face, acting as a large-area capacitor. The charges are arranged
as a double layer of opposite polarity on the opposing surfaces of the insulating sheet.
If one surface is already in contact with an earthed conductive plate (pipe wall or
reactor wall), the discharge is initiated by the approach of a grounded conductor.
Energy transfer: up to 100 J (100,000 mJ)

These discharges are energetic, and they can ignite most flammable gases and vapours
as well as most combustible powders. A person may suffer a serious shock when his
own body acts as the initiating electrode. Propagating brush discharges are not
possible if the breakdown voltage of the insulator is 4 kV or less.

The discharge pattern is always the same: many discharge channels branch off to
collect the charge from much of the surface. They all end on the approaching
conductor.
69
 Propagating brush discharge
(when an earthed electrode approached a highly charged insulating surface on
top of a metal plate)

The high surface charge densities necessary for propagating brush discharges cannot
be achieved by separation processes in manual operations such as wiping of insulating
surfaces or discharging a powder from a plastic bag.

Charging mechanisms associated with high separation velocity are necessary to build
up the high surface charge densities necessary for propagating brush discharges.

Examples of high-charge build-up industrial operations:

 high velocity pneumatic transfer of powder through an insulating pipe or a
conductive pipe with an insulating internal coating
 high velocity transportation of a highly insulating suspension through an insulating
pipe or a conductive pipe with an insulating internal coating
 fast rotation of conveyor or transmission belts made from insulating material or from
conductive material which is coated with an insulating material with high dielectric
strength
 filling of large containers or silos made from insulating materials (e.g. flexible
intermediate bulk containers) or of metallic containers or silos internally coated with
an insulating layer of high dielectric strength
 continuous impact of powder particles onto an insulating surface (e.g. a coated dust
deflector plate in a cyclone)

(3) Cone discharge (or conical pile discharge)

Cone discharge occurs along the surfaces of a pile of highly charged bulked insulating
powders or granules accumulated in silos, containers, and hoppers. It was first
observed in 1979 on polymeric granules. It can occur when filling powders or granules
into large containers and silos by pneumatic conveying system. Strong electric fields
result at the edge of the powder bed.

Cone discharges appears as a luminous, branched channel flashing radially from the
wall toward the center of the container if the height of the bed of powder is greater
than the silo radius.
70
Necessary conditions for cone discharge:
– powder with a high resistivity ( >1010 Ωm)
– high charge to mass ratio of the powder (when powder charged by pneumatic
transport)
– filling rate > 0.5 kg/s
– dust volumes > 1 m3

These discharges have energies up to several hundred mJ therefore they can ignite
flammable vapours, gases and dusts. Energy transfer: up to 1000 mJ

Pneumatic
conveying system

Charged
bulk powder

Cone discharge in a silo

(4) Brush discharge

It is a discharge between a relatively sharp-pointed conductor (radius of 5-50 mm) and
a charged nonconductive surface. The charges are in the form of a single charged layer
of one polarity. Brush discharge radiates from the conductor in a brush-like
configuration.

The nonconductive lining or surface must have a thickness greater than 2 mm. The
nonconductive coating can be a layer of powdered solid as well.

This discharge is less intense (max. 4 mJ) and is unlikely to ignite dusts, however can
ignite flammable vapours and gases.

Important differences between brush discharges and sparks:

(1) Since only part of a charged insulator contributes to the brush it is possible
to obtain many discharges from a single large charged surface.
(2) Because of the low mobility of charge carriers in an insulator, it is
impossible to remove the charge by simply connecting to ground.

71
 Several brush discharges generated at the surface of an earthed spherical
electrode

Examples of plant operations that are frequent sources of brush discharges:

 Approach of earthed conductive electrodes such as tools or a human fingertip to
highly charged insulating surfaces (e.g., plastic pipe for the conveyance of liquids or
dusts, plastic bags, common flexible intermediate bulk containers, plastic packing
drums or filter cloths as well as film webs, non-conductive conveyor belts or V-belts).
 Discharging of solids from plastic bags, or shaking out of plastic bags in the vicinity
of metal fittings (e.g. above an access port of a reaction vessel).
 Feeding of non-conductive liquids at high rate into a tank, approach of the charged
liquid surface to internal fittings, which can act as electrodes.
 Lowering of a conductive sampling beaker onto a highly charged liquid surface for
the purpose of taking samples.
 Projection of internal fittings into a highly charged dust cloud or a highly charged
droplet cloud.
 Charging of non-conductive powder into packing drums, containers or silos,
approach of the highly charged dust fill to the internal fittings or lowering of a
conductive earthed sample beaker for sampling or a level probe to determine the
level.

(5) Lightening-like discharge

It is a discharge from a cloud in the air over the powder. It does not occur in vessels
with volumes < 60 m3 or silos with diameter < 3 m.

(6) Corona discharge

It is similar to a brush discharge, but the electrode conductor has a sharp point (radius
< 0.5 mm like wires, sharp edges on electrodes etc). During corona discharge a current
flows from the sharp pointed electrode with a high potential into a neutral fluid (air) by
ionizing that fluid, creating a region of plasma around the electrode.

The energy of corona discharge (<< 0.2 mJ) is much lower than that of brush
discharges. The discharge can ignite only the most sensitive gases (e.g. H2).

72
 bluish glow

Conductor
(D <0.5 mm) Corona discharge Non-conductor

3.2.3 Energy from electrostatic discharges

A spark is generated between two conductors when the distance between them is small
compared to the diameter of the conductors and the electric field intensity between
them is greater than the breakdown voltage of air (3 MV/m). A brush discharge is
generated if the distance between the conductors is large compared to the radius of the
curvature of the conductor.

The minimum energy of a spark to ignite

– sensitive explosives: < 0.1 mJ
 H2 : 0.02 mJ
– mixtures of flammable vapours in air: 0.1-1 mJ
– fine flammable dusts: 1 – 50 mJ
– coarse flammable dusts: 40 – 1000 mJ

The electrical energy stored in a capacitor is the energy of a spark discharge. It can be
calculated as:
QV C V2 Q2
E  charge x potential difference   
2 2 2C
where E= energy of discharge process, J (Joule = Coulomb x Volt)
V= potential difference, V (Volt)
Q= charge, C (Coulomb)
Q
C= capacitance, F (Farad = Coulomb/Volt) and C
V

3.2.4 Streaming current

In industrial setting, the accumulated charge is usually the result of either contact or
friction charging for flowing solids and double-layer charging for flowing fluids. In
each case, the charge (electron) is transported with the material. The streaming current
is the flow of electricity by a charged flowing fluid or solid. This current is analogous
to a current in an electrical conduit.

The liquid streaming current is given by:

2   L 
I S  10 x 10  6 v D  1  exp    
  v τ 

where IS = streaming current, A (Ampere)

v= velocity of flow, m/s
D= diameter of pipe, m
L= length of pipe, m
τ= liquid relaxation time, s
73
The relaxation time is the time required for a charge to dissipate by leakage:

εr εo
τ
γc

where τ= relaxation time, s

εr = relative dielectric constant or relative permittivity, dimensionless
εo = 8.85x10 – 14 s/Ωcm = permittivity constant (permittivity of vacuum)
γc = specific conductivity, 1/Ωcm

The streaming current that is generated while transporting solids:

IS = charge build-up x mass flow rate

The charge build-up is a function of the solid processing method.

Charge Build-up for Various Operations

Process Charge build-up, Coulomb/kg
Sieving 10 – 9 - 10 – 11
Pouring 10 – 7 - 10 – 9
Grinding 10 – 6 - 10 – 7
Sliding down an incline 10 – 5 - 10 – 7
Pneumatic transport 10 – 5 - 10 – 7

Accepted Electrostatic Values for Calculations

Voltage to produce spark between needle points 12.7 mm apart 14 000 V
Voltage to produce spark between plates 0.01 mm apart 350 V
Maximum charge density before corona discharge 2.65x10 – 9 C/cm2
Minimum ignition energies
Vapour in air 0.1 mJ
Mist in air 1.0 mJ
Dusts in air 10.0 mJ
Approximate capacitances
Humans 100-400 pF
Automobiles 500 pF
Small scoop, tools 5 pF
Small metal items (scoop, hose nozzle, etc.) 10-20 pF
Buckets, small drums 20 pF
Small containers (buckets, 50 liter drum) 10-100 pF
200-400 liter containers 100 pF
Medium containers (250-500 liter drums) 50-300 pF
3
7.6 m tank truck 1 000 pF
3.6 m diameter insulated tank 100 000 pF
Capacitance between two 5 cm flanges 20 pF
Major plant items (reactor vessels) 100-1000 pF
pF is pico Farad; 1 pF = 10 – 12 F

74
3.2.5 Electrostatic voltage drops
A fluid flows through the feed line and drops into a tank. The streaming current builds
up a charge and voltage in the feed line to the vessel and the vessel itself.

1 Metal pipe
Glass lined pipe

Glass vessel

The voltage from the electrical ground in the metal line to the end of the glass pipe
(from point 1 to 2) is calculated as:
L
V = IS R and R
γc A

where V= voltage build-up, V

IS = streaming current, A (Ampere)
R= resistance, Ω
L= length of non-conducting pipe between point 1 and 2, m
A= cross-sectional area of pipe, cm2
γc = specific conductivity of the fluid, 1/Ωcm

3.3 Controlling static electricity

Charge build-up, resulting sparks, and the ignition of flammable materials is an
inevitable event if control methods are not appropriately used. Design engineers install
special features to prevent
(1) sparks by eliminating the build-up and accumulation of static charge
(2) ignition by inerting the surrounding.

Inerting is the most effective and reliable method for preventing ignition. It is always
used when working with flammable liquids that are 5°C or less below the closed cup
flash point.

General design methods to prevent electrostatic ignitions

The design objective is to prevent the build-up of charges on a product (liquid or
powder) as well as on surrounding objects (equipment or personnel).

75
3 methods are used to achieve the objective:
(1) Prevent charges from accumulating to dangerous levels by reducing the rate
of charge generation and increasing the rate of charge relaxation. This
method is generally used when handling liquids.
(2) Prevent charges from accumulating to dangerous levels by using charge
reduction by low-energy discharges. This method is generally used when
handling powders.
(3) Prevent the possibility of ignition by maintaining O2 levels below the
combustible levels (inerting) or by maintaining fuel levels below the LFL or
above the UFL. Measures to mitigate the consequences of an explosion are
also options (e.g. deflagration venting, explosion suppression).

Special design features:

Sparks are prevented by grounding and bonding. This procedure prevents two
metallic objects (close to each other) from having different potentials. It prevents the
existence of isolated metal parts or objects, which are notorious for building up large
potentials and energetic sparks.

Propagating brush and brush discharges are prevented by keeping the nonconductive
surfaces or coatings thin enough or conductive enough to have breakdown voltage
below 4 kV.

Cone discharges are prevented by increasing the conductivity (additives), by

decreasing the charge rate below 0.5 kg/s or by using containers with a volume less
than 1 m3. Inerting is the most effective way of preventing ignition from conical piles.

 The use of insulating materials should be reduced as much as possible

(packaging, equipment, piping etc).
 Highly insulating filter cloths should not be used in open systems.
 Funnels, pumps, and the like with insulating properties should not be used in
the handling of flammable liquids with conductivities of 108 1/Ωm or less.
Relaxation
When pumping fluids into a vessel through a pipe on top of the vessel, the separation
produces a streaming current and charges build up. This hazard can be substantially
reduced by adding an enlarged section of pipe just before entering the tank. This hold
provides time for charge relaxation. The residence time in this relaxation section of
pipe should be about twice the relaxation time determined by calculation. In actual
practice, a hold time equal to or greater than half the relaxation time is sufficient to
eliminate charge build-up.

The American Petroleum Institute (API) recommends vD < 0.5 m2/s for road tanker
filling.

 Relaxation pipe should be installed as necessary.

 After a container is transported, relaxation time should be taken.

76
Bonding and grounding
Historically there was little problem when piping was all copper, stainless steel or iron.
The problem comes when pipes or vessels are glass or Teflon lined or made from
polymers or connected with non-conducting gaskets. There has always been a problem
when pouring either liquid or a solid through an open space (i.e. a filling operation).

The potential difference between two conductive materials is reduced to zero by

bonding the two materials, that is, by bonding one end of a conductive wire to one end
of the materials and bonding the other end to the second material.

Grounding is an electrical connection with the earth.

Earthing all conductive parts that might be dangerously charged is not enough, if non-
conductive parts and materials are present. In such cases dangerous charging of
nonconductive parts and substances (including solids, liquids, and dusts) has to be
excluded.

Different bonded sets of materials may have different potentials. The potential
difference between sets is reduced to zero by grounding each set.

Filling liquid from a drum

Bonding and grounding procedures for tanks and vessels

Examples: (Events happened at BASF and Dow Chemical)

Solid filling operation
Situation #1: A non-conductive bulk
product is fed out of 25 kg PE-
bags in a vessel, in which a
flammable liquid is being stirred.
During shaking of the just
emptied bag an ignition occurred.
Cause: All handling of non-conductive
solids or bulk products may
generate static electricity. Due to
contact charging of the sliding
bulk product, both the bulk
product and non-conducting
package materials became
charged. Brush discharges form
the surface of the powder had
ignited the vapour/air mixture.

77
Precaution: Either fill into a closed, inerted vessel or avoid charge generation.
Situation #2: An operator filled a non-conductive bulk product out of 25 kg PE-bags in a
solvent free mixer. Exhaust system operated. All equipment grounded, the floor was
dissipative, the operator wore dissipative footwear. During pouring the product in the
reaction vessel explode.
Cause: The plastic wrap that held the sacks on the pallet was on the floor and the operator
was standing on it. This allowed a static charge to build up in him.
Precaution: Always guarantee ground connection.

Lined metal drum filling

Situation #3: A pure liquid was filled in a steel
drum with an inner plastic liner. To avoid
splash filling a short funnel was inserted in
the spout. The nozzle, the drum, and the
weighing machine were all grounded.
Despite having an exhaust system there was
an explosion during drum filling.
Cause: Electrostatic charge generation at the
surface of the non-conductive coating cannot
be transferred. The funnel had sufficient
capacitance was insulated from the ground
by the PE lined filler cap. Spark discharge
from funnel caused explosion.
Precaution: Guarantee ground connection of all
conductive equipment.

PE-drum filling
Situation #4: A mixture of water and hydrocarbon was
separated; the water phase was released from
time to time into a PE-drum located below the
separator. During such a release a fire occurred
on top of the PE-drum.
Cause: Splash filling the PE-drum generated charge
accumulation at the wall material. The
unintended release of a small amount of
hydrocarbon generated a flammable atmosphere
in the drum and an ignition by brush discharges
occurred.
Precaution: Install a level indicator so that an
unintended release of hydrocarbons does not
occur.

78
Liquid agitation
Situation #5: After intense mixing, a non-conductive
flammable dispersion was poured from the
mixing vessel into a PE-drum just positioned
below. The exhaust system was in operation,
and to avoid charge accumulation a grounded
rod was inserted. During drum filling a fire
occurred.
Cause: Intense stirring of non-conductive liquids or
multiphase liquids leads to charge
accumulation. Splash filling in the non-
conductive drum led to high charge
accumulation on the inner walls of the drum
and brush discharges from wall to grounded
rod.
Precaution: Need to have another exhaust system
and filling method since an explosive
atmosphere and static electricity are formed at
the same time in the same location.

Super sack filling operation

Situation #6: A reactor vessel was
purged with N2 and feeding
toluene was started. During the
feeding operation, a resin was
prepared for pouring from an
“antistatically treated” super
sack via the filling port. The
exhaust system was operating.
Just at the beginning of pouring
the bulk product into the vessel,
an explosion occurred.
Cause: Charge build up was
generated both by splash filling
the liquid and by pouring the
bulk product. Flammable
atmosphere in the gas space of
the vessel was avoided by N2
purging, but the fast release of
the bulk product ejected
toluene/dust/N2 mixture up into
the air where ignition occurred
from either a spark discharge from the charged-insufficiently treated-super sack or
charged operator by brush discharge.
Precaution: Only packaging with sufficient antistatic treatment should be used.

79
Maintenance of a lever indicator
Situation #7: A level indicator at a pressurized vessel
was blocked. Usual maintenance procedure is
the fast release of product in a pail until the
connection between indicator and vessel is
cleared. During such a procedure, a fire
occurred and two persons were injured.
Cause: The release of a pressurized liquid generates
highly charged droplets thus generating both
an explosive atmosphere in the surrounding
and brush discharges between the opened valve
and the surface of the non-conducting pail
used.
Precautions: For effective cleaning a fast release is
required. To avoid ignition the procedure needs
to be changed to discharge the pressure in a
waste gas collecting system.

Those who ignore history are doomed to repeat it.

Dip legs
An extended line, called dip leg or dip pipe, reduces the electrical charge that
accumulates when liquid is allowed to free fall. When using dip pipes, care must be
taken to prevent siphoning back when the inlet flow is stopped. This is achieved by
placing a hole in the dip pipe wall near the top of the vessel. An angle iron can also be
used instead of a dip pipe.

Hole for
○ siphon break

Dip leg
Angle iron

Liquid Liquid

Dip leg and angle iron to prevent free fall and accumulation of static charge
Increasing conductivity with additives
The conductivity of non-conducting organic materials can sometimes be increased by
using antistatic additives. Examples are water and polar solvents such as alcohols.
Water is effective only when it is soluble in the liquid, because an immiscible phase
gives an additional source of charge separation and build-up.

80
 Handling solids without flammable vapours
Charging solids with a non-grounded and conductive chute can result in a build-up of a
charge on the chute. This charge can accumulate and finally produce a spark that may
ignite a dispersed and flammable dust.

Solids are transferred safely by bonding and grounding all conductive parts and/or by
using nonconductive materials for the drum and chute.

Bonds and grounds

Ground

Ground

Handling solids without flammable vapours present

Handling solids with flammable vapours
A safe design for this operation includes enclosed handling of the solids and liquids in
inert atmosphere. For solvent-free solids, the use of nonconductive containers is
permitted. For solids containing flammable solvents, only nonconductive and
grounded containers are recommended.

Bonds and ground

Charge container closed
Solids and purged with N2
before opening valve
N2

Rotary valve
N2 Shutoff valve
Shutoff valve
Bond all gasketed flanges

Liquid Liquid
Ground

Handling solids with flammable vapours present

81
3.4 Explosion-proof equipment and instruments
All electrical devices are inherent ignition sources. Special design features are required
to prevent ignition of flammable vapours and dusts. The fire and explosion hazard is
directly proportional to the number and type of electrically powered devices in a
process area.

Process areas are divided into two major types of environment:

(1) XP (explosion proof)—flammable materials (particularly vapours) might be
present at certain times.
(2) Non-XP—flammable materials are not present even under abnormal
conditions. In these areas open flames, heated elements and other sources of
ignition may be present.

Explosion-proof housings
In an XP area, the electrical equipment and some instrumentation must have special
explosion-proof housing. The housings are not designed to prevent flammable vapours
and gases from entering but are designed to withstand an internal explosion and
prevent the combustion from spreading beyond the inside of the enclosure. E.g. a
motor starter is enclosed in a heavy cast walled box that can withstand explosive
pressures.
Area and material classification
Hazardous area classification is a method of analysing and classifying the environment
(areas or zones) within a plant according to the likelihood of flammable gas or vapour
concentrations being present. Electrical equipment and instrumentation should be
safety certified to the appropriate level before they can be used in certain zones.

The starting point is to identify sources of release of flammable gas or vapour. These
may arise from constant activities; from time to time in normal operation; or as the
result of some unplanned event. In addition, inside process equipment may be a
hazardous area, if both gas/vapour and air are present, though there is no actual
release.

In Europe:
Hazardous areas are classified into zones based on an assessment of the frequency of
the occurrence and duration of an explosive gas atmosphere.

The zone defines the probability of hazardous material being present in an ignitable
concentration in the surrounding atmosphere.

An area in which an explosive gas-air mixture is continuously present or

Zone 0
present for long periods.
An area in which an explosive gas-air mixture is likely to occur in normal
Zone 1
operation.
An area in which an explosive gas-air mixture is not likely to occur in
Zone 2 normal operation and, if it does occur, will only exist for a very short time
due to abnormal condition.

82
Example:
A process vessel in which flammable solvents are being mixed within a building located at an
industrial site. The inside of the vessel can be classified as Zone 0. The building containing
the vessel may be Zone 1 (as the vessel may be opened from time to time and drums of solvent
or solvent pipes may be present). The area outside the building would normally be classified
as Zone 2 providing sensitive flammable atmosphere could not be generated from other
sources.

Another example:

Hazardous area classification is similarly applied to the presence of flammable dust. In

this case the zones 0, 1, and 2 becomes zones 20, 21, and 22, respectively.

Highly insulating surfaces, such as plastics are prohibited from use in zones 0 and 1.

In the USA
The rating method includes:
– Classes I, II, and III
– Groups A-G
– Divisions 1 or 2
(define the general nature of hazardous material)
(define the hazardous material)
(define the probability of hazardous material being
present in ignitable concentration)

The classes are related to the nature of the flammable material:

– Class I: Locations where flammable gases or vapours are present
– Class II: Same for combustible dusts
– Class III: Locations where combustible fibers and dusts are present but not
likely to be in suspension

The groups designate the presence of specific chemical types. Chemicals that are
grouped have equivalent hazards.
– Group A: acetylene
– Group B: H2, ethylene, butadiene, propylene oxide, ...
– Group C: CO, H2S, ether, cyclopropane, ...
– Group D: butane, ethane, ethanol, methanol, acetone, benzene, petrol, hexane,
natural gas, NH3
– Group E: Al dust , combustible metal dusts (Al, Mg, their alloys)
– Group F: carbon black, coke dust, coal dust
– Group G: flour, sugar, wood, plastic, grain dust, ...

83
Divisions indicate the probability of the material being within the flammable or
explosive region.
– Division 1: Probability of ignition is high; that is, flammable concentrations
are normally present
– Division 2: Hazardous only under abnormal conditions. Flammable
materials are normally contained in closed containers or systems.

When designing an XP area, all pieces of electrical equipment and instrumentation are
specified for the class, group, and division. The overall classification is only as good
as the piece of equipment in an area with the lowest classification.

3.5 Ventilation
Proper ventilation is another method used to prevent fires and explosions. The purpose
of ventilation is to dilute the explosive vapours with air to prevent explosion and to
confine the hazardous flammable mixtures.

Open-air plants are recommended because the average wind velocities are sufficient to
safely dilute volatile chemical leaks that might exist within a plant. Although safety
precautions are taken to minimize leaks, accidental leaks from pump seals and other
potential release points are possible.

Frequently, processes cannot be constructed outside. In this case, local and dilution
ventilation systems are required. Local ventilation (a hood) is the most effective
method for controlling flammable gas releases.

3.6 Sprinkler systems

Sprinkler systems are effective way to contain fires. The system consists of an array of
sprinkler heads connected to a water supply. The heads are mounted in a high location
(usually near ceilings) and disperse a fine spray of water over an area when activated.
The heads are activated by a variety of methods. Once activated, the sprinklers cannot
be turned off unless the main water supply is stopped. These systems are used in
storage areas, laboratories, control rooms, and small pilot areas.

Sprinkler systems can cause considerable water damage when activated, depending on
the contents of the building; however, the water damage is always smaller than the
damage from the fire could be.

Sometimes vessels need special water protection to keep the vessel walls cool during
fires. High surface temperatures can result in metal failure at pressures far below the
vessel’s maximum allowable working pressure. In hydrocarbon spill fires unprotected
vessels (no insulation or water spray) can fail within minutes.

84
3.7 Reliefs
Despite many safety precautions within chemical plants, equipment failure or operator
errors can cause increases in process pressures beyond safe levels. If pressures rise too
high, they may exceed the maximum strength of pipelines and vessels. This can result
in rupturing of process equipment, causing major releases of toxic or flammable
chemicals.

The defence against this type of accident is:

1.) prevent the accident in the first place by inherent safety,
2.) better process control,
3.) install relief systems to relieve liquids or gases before excessive pressures
are developed.

The relief system is composed of the relief device and the associated downstream
equipment to safely handle the material ejected.

Relief systems include:

– pipe to the relief
– relief device
– discharge pipeline
– knockout drum
– scrubber
– flare

Guideline for relief positions:

– All vessels need reliefs (reactors, storage tanks, towers, drums).
– Positive displacement pumps, compressors, and turbines need relief on the
discharge side.
– Storage vessels need pressure and vacuum reliefs to protect against pumping
in or out of a blocked-in vessel or against the generation of a vacuum by
condensation.
– Vessel jackets are often rated for low-pressure steam. Releifs are installed in
jackets to prevent excessive steam pressure.
– Block-in sections (in which liquid is not flowing) of cool liquid-filled lines
that are exposed to heat (such as the sun) or refrigeration.
Relief types
Specific types of relief devices are chosen for specific applications (for liquids, gases,
liquids and gases, solids, or corrosive materials). They may be vented to the
atmosphere or vented to containment systems (scrubbers, flare, condenser, incinerator
etc.).

There are two general categories of relief valves:

(1) Spring operated, and
(2) Rupture disc.

85
On spring-operated valves, the adjustable spring tension offsets the inlet pressure. The
relief set pressure is usually 10% above normal operating pressure.

Rupture discs are specially designed to rupture at a specified relief set pressure.
Rupture disc remains open once it opened. This may lead to the complete discharge of
process material. It may also allow air to enter the process, leading to possible fire and
explosion. Rupture discs are available in much larger sizes than spring-operated relief
valves and cost less.

Rupture discs are frequently installed in series before a spring-loaded relief to

– protect the spring-loaded device from corrosive materials
– protect the relatively complex parts of a spring-loaded device from reactive
monomers that could plug it
– give absolute isolation when handling extremely toxic chemicals (spring-
loaded reliefs may weep)
– give absolute isolation when handling flammable gases
– relief slurries that may plug spring-loaded devices.

When rupture discs are used before a spring-loaded relief, a pressure gauge is installed
between the two devices. It will show when the disc ruptures or leaks because of
pinhole caused by corrosion. In either case, it indicates when the disc needs to be
changed.

86
Horizontal knockout drum (blowdown drum)
The horizontal knockout drum serves as a vapour-liquid separator as well as a holdup
vessel for the disengaged liquid.

Vapour to condenser,
flare, or scrubber

Rapture disc

Reactor

Blowdown drum

Relief containment system with blowdown drum

For environmental considerations, reliefs now rarely vented to the atmosphere. In most
cases, a relief is first discharged to a knockout drum to separate the liquid from the
vapour; here the liquid is collected and the vapour is discharged to another treatment
unit. This type of system is called total containment system. They are commonly
used and they are becoming an industrial standard.
Flares
Flares burn the combustible or toxic gas to produce combustion products that are
neither toxic nor combustible.
Scrubbers
Scrubber can be packed or plate columns, or Venturi scrubbers. (Details of scrubber
design: Treybal: Mass transfer operation.)

3.8 Emergency fire fighting

Fire temperatures for various materials (wood, plastic, solvents) is about 1000°C.
Hydrocarbon fires temperatures are about 1200°C. Steel weakens at ~ 575°C;
therefore, steelwork may be completely distorted in a fire. Aluminium and its alloys
have very low melting point (~ 660°C). All aluminium products will therefore melt
during fires.

Larger appliances used exclusively by fire brigades include: mobile pumps, mobile
turntables (fire engine), platforms, extension ladders, rescue and demolishing
equipment.

87
Equipment handled by normal works personnel include:

Fixed extinguishers
Fixed extinguishers for manual or automatic operation using water or high expansion
foam for general protection. For oil or electric fire, other extinguishing agents are
used.

Hose reels
A hose reel has a non-kinking rubber tubing of 20-25 mm diameter up to 35 m long. A
valve and nozzle are attached to the free end of the hose, which is wound on a metal
reel. Nozzles should give a minimum flow of about 23 liter/min.

Hydrants
Hydrants are arrangements of piping and outlets to which large diameter hose (65 mm
or more) may be connected for use by the fire brigade or works firemen.

Automatic sprinklers
These consists of a system of pipes, spray nozzles and heat operated valves by means
of which a fire is automatically detected, the alarm given and water delivered to the
fire. Sprinklers are useful for stores, laboratories, control rooms and other buildings
containing combustible materials, which are left unattended. Similar systems may also
be used on the outside of buildings to keep them cool if a fire develops near them.

High expansion foam

The system consists of one or more foam-making machines fitted with short rigid
ducts. The foam is of very low density but sufficient stability not to collapse at once
when exposed to fire. Its action is to smother and blanket the fire.

High pressure water spray (fog)

The water is delivered at high pressure through special nozzles to form fine droplets.
The high-pressure water spray requires the use of special booster pump (carried by
most fire brigades) which gives pressure of ~ 50 atm. Its main use is for fires of
flammable liquids and gases. It removes the main disadvantages of water in dealing
with such fires.

Medium expansion foam

CO2 and other inert gases

Gas extinguishing systems consist of a supply of inert gas under pressure (usually in
cylinders), a system of pipework, a valve delivering the inert gas to the points of
application, and an automatic detection and initiating system which opens inert gas
valves ones the fire has been detected. It also closes doors and ventilation ducts.

These systems operate by reducing the O2 content of the air and/or by interrupting the
chemical reaction in a flame.

It is suitable for electrical fires and flammable liquid fires.

88
Dry powder
Various free-flowing powders are used to pour over a fire to extinguish it. The
compositions of many fire-extinguishing powders are not published by their
manufacturers.

They generally contain 3 principal ingredients:

(1) Sodium or potassium bicarbonate (NaHCO3, KHCO3)
These liberate CO2 when heated: NaHCO3 → Na2CO3 + CO2 +H2O
They also react with and neutralize acids:
NaHCO3 + HCl → NaCl + CO2 + H2O
(2) Certain finely powdered salts of metals
When they are present as a dust in the air, strongly absorb radiant heat,
thereby cooling and in some cases extinguishing flames.
(3) A compound, which prevents the powder particles from adhering to one
another and forming lumps.

Dry powder installations comprise a dry powder container to which a gas cylinder
(usually CO2) is coupled, and a system of piping and outlets, which are located above
the places where fires are likely to break out.

They are suitable for flammable liquids and electrical equipment.

Portable fire extinguishers

They can deliver water, foam, dry powder, or CO2 to the seat of a fire.

In the European Union, the standard requires that all fire extinguishers should have a
red body and have a band of a second colour covering between 5-10% of the surface
relating to the extinguisher’s contents.

There is no official standard in the United States for the colour of fire extinguishers.
Extinguishers are marked with pictograms depicting the types of fires that the
extinguisher is approved to fight.

Colour Identification of Portable Fire Extinguishers

Type EU Australia USA Suitable for use
on fire classes
Water red red silver A
Foam cream blue A, B
Dry powder blue white A, B, C, E
CO2 black black (A), B, D, F,

89
3.9 Chemical reactivity
Although accidents attributed to chemical reactivity are less frequent compared to fires
and explosions, the consequences are dramatic and destructive. When working with
chemicals, the potential for unwanted, unexpected, and hazardous reactions must
always be understood, including potential side reactions, decomposition reactions, and
reactions resulting from the accidental and wrong combination of chemicals or
reaction conditions (wrong concentration, wrong temperature).

Preliminary indication of the potential hazard can be estimated by knowing the

chemical structure of materials. Functional groups that contribute to the explosive
properties of a chemical through rapid combustion or detonation are listed in the next
table.

Peroxides and peroxidizable compounds are dangerous sources of explosions.

Structures of peroxidizable compounds are given in the next three tables.

When peroxide concentration increases to ≥ 20 ppm, the solution is hazardous.

90
Reactive Functional Groups
Name of functional group Chemical formula
Azide – N3
Diazo –N=N–
Diazonium – N2+ X –
Nitro – NO2
Nitroso – NO
Nitrite – ONO2
Fulminate – ONC
Peroxide –O–O–
Peracid – CO3H
Hydroperoxyde – O – O –H
Ozonide O3
N-haloamine – N– Cl

X
Amine oxide  NO
Hypohalites – OX
Chlorates ClO3
Acetylides of heavy metals – C  CM

91
Peroxidizable Compounds
Organic material Structure
Ethers, acetals –C–O–

Olefins with allylic hydrogen, chloro- and >C=C<
fluoroolefins, terpens, tetrahydronaphtelene
Dienes, vinyl acetylenes  
>C=C–C=<

> C = C – C  CH

Paraffins and alkyl-aromatic hydrocarbons, >C–
particularly those with tertiary hydrogen 
H
Aldehydes –C=O

H
Ureas, amides, lactones O H
  
–C–N–C
Vinyl monomers, including vinyl halides, 
acrylates, methacrylates, vinyl esters >C=C–
Ketones having and alpha-hydrogen –C–C<
 
O H
Inorganic compounds
Alkali metals, particularly potassium
Alkali metal alkoxides and amides
Organometallics

92
Examples of Peroxidizable Compounds
Peroxidizable hazard on storage Isopropyl ether
Divinyl acetylene
Vinilidene chloride
Potassium metal
Sodium amide
Peroxidizable hazard on concentration Diethyl ether
Tetrahydrofuran
Dioxane
Acetal
Methyl i-butyl ketone (MIK)
Ethylene glycol dimethyl ether (glyme)
Vinyl ethers
Decyctapentadiene
Diacetylene
Methyl acetylene
Tetrahydronaphthalene
Cyclohexane
Methylcyclohexane
Hazardous when exposed to O2 due to Styrene
peroxide formation and subsequent initiation Butadiene
of polymerization Tetrafluoroethylene
Chlorotrifluoroethylene
Vinyl acetylene
Vinyl acetate
Vinyl chloride
Vinyl pyridine
Chloroprene

Reaction hazard index (RHI)

Reaction hazard index is a rating system to establish the relative potential hazards of
specific chemicals. It is related to the maximum adiabatic temperature reached by the
products of a decomposition reaction.

10 Td
RHI 
Td  30 E a

where Td = decomposition temperature, K

Ea = Arrhenius activation energy, kcal/mol

RHI has a low value (1-3) for relatively low reactivities and higher value (5-8) for high
reactivities.

93
 Reaction Hazard Index Data
Compound Formula T d, T d, Ea, RHI
°C K kcal/mol
Chloroform CHCl3 590 863 47 3.26
Ethane C2H6 324 597 89.5 1.82
Toluene C 7H 8 586 859 85 2.52
Acetic acid CH3COOH 361 634 67.5 2.38
Propylene C 3H 6 583 866 78 2.70
i-propyl ether (CH3)2CHOCH(CH3)2 (C6H14O) 439 712 63.5 2.72
Ethylene C 2H 4 732 1005 46.5 4.19
1,3-butadiene CH2=CHCH=CH2 (C4H6) 718 991 79.4 2.94
Vinyl ethyl ether CH3CH2-O-CH=CH2 (C4H8O) 607 880 44.4 3.98
Styrene C6H5CH=CH2 (C8H8) 720 993 19.2 6.33
Hydrazin NH2NH2 (N2H4) 1065 1338 60.5 4.25
Ethylene oxide (CH2CH2)O (C2H4O) 789 1062 57.4 3.81
Vinylacetylene HC≡C-CH=CH2 (C4H4) 2044 2317 28.0 7.33
Cellulose nitrate C12H16N4O18 1940 2213 46.7 6.12
Acetylene CHCH (C2H2) 2625 2898 40.5 7.05
Nitroglycerine C3H5(ONO2)3 2622 2895 40.3 7.05
Diethyl peroxide CH3CH2-O-CH(O-OH)-CH3 695 968 37.3 4.64

3.10 Lessons learned from accidents

Static electricity
– Operators must be cautioned against drawing pipes or tubing through their rubber
gloves, resulting in static build-up.
– Clothing that generate static electricity must be prohibited.
– Recirculation lines must be extended into the liquid to prevent static build-up.
– Shoes with conductive soles are required when handling flammable materials.
– Bonding, grounding, humidification, ionization, or combinations are recommended
when static electricity is a fire hazard.
– Inert gas blankets must be used when handling flammable materials.
– Drums, scoops, and bags should be physically bonded and grounded.
– Ground connections must be verified with resistance testers.
– Spring-loaded grounding or bonding clips should be replaced with screw type C-
clamps.
– Conductive grease should be used in bearing seals that need to conduct static
charges.
– Stainless steel centrifuges must be used when handling flammable materials.
– Flanges in piping and duct systems must be bonded.

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Chemical reactivity
– It is important to understand the reactive properties of chemicals before working
with them.
– If data is not available in literature, experimental testing is necessary.
– Data of special importance include decomposition temperatures, rate of reaction or
activation energy, impact shock sensitivity, and flash point.
– Accidents occur rapidly, usually there is no time to manually return the system to
control once the accident is in progress.
– The system designs required for preventing an accident are frequently requiring
only minor process changes.
– Use the appropriate materials of construction, especially when using old systems for
new applications.
– Do not install pipes underground, in pits, trenches, or depressions where water can
accumulate.
– Be sure of the quality of construction (e.g. welds) meets the required specifications.
– Check all purchased instruments and equipment for integrity and functionality.
– Do not secure pipe too rigid. Pipes must be free to expand so they will not damage
other parts of the system.
– Do not install liquid-liquid flanges above electrical cables since leakage can occur.
– Do not use screwed joints and fittings when handling hazardous chemicals.
– Be sure that all that can catch water can be properly drained
– Do not install traps in lines where water can collect and develop corrosion problem.
– Install bug screens on vent lines.
– Critical safety instruments must have backups.
– Provide block valves for emergency shutdowns.
– Safety procedures and standard operating procedures are needed.
– Never use gas to open plugged lines.
– Train operators and maintenance personnel to understand the consequences of
deviations from the norm.
– Make periodic and precise audits of procedures and equipment.

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