Kathmandu University

Chemical Process Safety

Introduction

Dr. Ziaul Haque Ansari

Department of
Chemical Science and Engineering
Table of Contents

Safety Programs
The Nature of the Accident Process
Inherent Safety
Four Significant Disasters
Flixborough, England
Bhopal, India
Seveso, Italy
Pasadena, Texas
Safety Practices in Chemical Industries

Economics of safety

Culture of safety

Awareness of safety

Training is essential

Provide visual aids

Use of right ppe [Personal Protective Equipment]

Safety Practices in Chemical Industries
General safety

Occupational safety and health

Process and production safety

Material safety

Workplace safety

Fire safety

Electrical safety

Building and structural safety

Environmental safety
Safety Practices in Chemical Industries
ABC of workplace safety

• A-Attention

• B-Behavior

• C-Control

Identify hazard: risk associated with it

Analyze and evaluate

Determine appropriate way to eliminate hazard

Safety Practices in Chemical Industries
Plant safety catogories

• Short time scale: acute problems

• Long time scale: chronic problems

Plant safety deals with

 Cognitive process : thought, experience, senses

 Human behavior

 Fluid mechanics of reactive flows

Safety Practices in Chemical Industries
We have issues such as

• How to motivate operators to behave

• How to design a control room

• How to build intrinsic safety into a process

• How to control overpressure

• How to consequence of pipe failure

• How to prevent explosion

Safety Practices in Chemical Industries
Plant safety one has to be selective

• Types of accident

• Problem encountered recently in industry

Definitions

Safety

The condition of being safe; freedom from danger, risk or injury.

Reliability

The probability that a component part, equipment, or system will

satisfactorily perform its intended function under the given
circumstances for a specified period of time.
Definitions
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Much more recently, "safety" has been replaced by "loss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 the design of new engineering features to prevent
loss.

The subject of this text is loss prevention, but for convenience,

the words "safety“ and "loss prevention" will be used
synonymously throughout.
Definitions
 Safety, hazard, and risk are frequently-used terms in chemical
process safety. Their definitions are

 Safety or loss prevention: 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: a measure of human injury, environmental damage, or

economic loss in terms of both the incident likelihood and the
magnitude of the loss or injury.
Safety Programs
A successful safety program requires several ingredients.

These ingredients are:

 System
 Attitude
 Fundamentals
 Experience
 Time
 You
The Nature of the Accident Process
 Chemical plant accidents follow typical patterns.

 fires,
 explosion and
 toxic release.

With respect to fatalities,

the order reverses, with toxic release
having the greatest potential for
fatalities.
The Nature of the Accident Process
Most accidents follow a three-step sequence:

 initiation (the event that starts the accident),

 propagation (the event or events that maintain or expand the
accident), and
 termination (the event or events that stop the accident or
diminish it in size).

Example:
 The worker tripped to initiate the accident.
 The accident was propagated by the shearing of the valve and
the resulting explosion and growing fire.
 The event was terminated by consumption of all flammable
materials.
The Nature of the Accident Process
Example 1-6

The following accident report has been filed:

Failure of a threaded 1%" drain connection on a rich oil line at the base
of an absorber tower in a large (1.35 MCFID) gas producing plant
allowed the release of rich oil and gas at 850 psi and -40°F. The resulting
vapor cloud probably ignited from the ignition system of engine driven
recompressors. The 75' high X 10' diameter absorber tower eventually
collapsed across the pipe rack and on two exchanger trains. Breaking
pipelines added more fuel to the fire. Severe flame impingement on an
11,000-horsepower gas turbine-driven compressor, waste heat recovery
and super-heater train resulted in its near total destruction.
Identify the initiation, propagation, and termination steps for this
accident.
The Nature of the Accident Process
Solution 1-6

Initiation: Failure of threaded 172" drain connection

Propagation: Release of rich oil and gas, formation of vapor

cloud, ignition of vapor cloud by recompressors,
collapse of absorber tower across pipe rack

Termination: Consumption of combustible materials in process

Major Chemical Industry Accidents
The study of case histories provides valuable information to
chemical engineers involved with safety.

This information is used to improve procedures to prevent similar

accidents in the future.

The four most cited accidents

 Flixborough, England;
 Bhopal, India;
 Seveso, Italy; and
 Pasadena, Texas
Major Chemical Industry Accidents
June 1, 1974: Flixborough disaster, England. An explosion at a
chemical plant near the village of Flixborough kills 28 people and
seriously injures another 36.

July 10, 1976: Seveso disaster, in Seveso, Italy, in a small

chemical manufacturing plant, due to the release of dioxins into
the atmosphere, 3,000 pets and farm animals died and, later,
70,000 animals were slaughtered to prevent dioxins from entering
the food chain.
Major Chemical Industry Accidents
In addition, 193 people in the affected areas suffered from
chloracne and other symptoms. The disaster lead to the Seveso
directive, which was issued by the European Community and
imposed much harsher industrial regulations.

November 19, 1984: San Juanico, Mexico LPG Disaster, a gas

leak in stored LPG set off a gas cloud which drifted towards
houses, ignited and caused BLEVE, rupturing large spheres and
many cylinders 500 deaths, unknown number of burn victims
Major Chemical Industry Accidents
December 3, 1984: The Bhopal disaster in India is the Worst and
Largest industrial disaster on record. A faulty tank containing
poisonous methyl isocyanate leaked at a Union Carbide plant and
left nearly 4,000 people dead on the first night of the gas leak and
at least 15,000 later from related illnesses. The disaster caused the
region's human and animal populations severe health problems to
the present.

October 23, 1989: Phillips Disaster. Explosion and fire killed 23

and injured 314 in Pasadena, Texas. Capital losses over $715
million.
1. Flixborough disaster, England
The chemical plant in operation since 1967, produced
caprolactam, a precursor chemical used in the manufacture of
nylon.

The process involved oxidation of cyclohexane with air in a series

of six reactors to produce a mixture of cyclohexanol and
cyclohexanone.

Two months prior to the explosion, a crack was discovered in the

number 5 reactor. It was decided to install a temporary 50 cm
diameter pipe to bypass the leaking reactor to allow continued
operation of the plant while repairs were made.
1. Flixborough disaster, England
At 17:00 hrs on Saturday 1 June 1974, the temporary bypass pipe
(containing cyclohexane at 150°C and 1 MPa (10 Bar)) ruptured,
possibly as a result of a fire on a nearby pipe which had been
burning for nearly an hour. Within a minute, about 40 tons of the
plant's 400 tons store of cyclohexane leaked from the pipe and
formed a vapour cloud 100–200 meters in diameter. The cloud, on
coming in contact with an ignition source (probably a furnace at a
nearby hydrogen production plant) exploded, completely
destroying the plant.
1. Flixborough disaster, England

Around 1,800 buildings within a mile radius of the site were

damaged.

Observers have said that had the explosion occurred on a weekday,

more than 500 plant employees would likely have been killed.
Resulting fires raged in the area for over 10 days.
1. Flixborough disaster, England

A failure of a temporary pipe section replacing reactor 5 caused

the Flixborough accident
1. Flixborough disaster, England

A
2. Bhopal - India
Bhopal is the capital of a less developed
Madhya Pradesh

70’s period of green revolution–large scale

use of fertilizers & pesticides

Import of pesticides costly, indigenous

production encouraged

Incentives for industrial development

1969 - UCIL subsidiary of UCC set up

pesticide plant to make Carbaryl in using imported raw materials

1979 – granted licence to make MIC based pesticides

1980 – production started

2. Bhopal – India
 Refrigeration Unit
Union Carbide  Vent Gas Scrubber
 Flare Tower
 Water Curtain
 Alarm Siren
2. Bhopal – India
Methyl Isocyanate Storage Tank
2. Bhopal – India
Bhopal - the World's Worst Industrial Disaster

The Bhopal disaster, also known as the Union Carbide disaster or

the Bhopal gas tragedy, was an industrial catastrophe that took place
at a Union Carbide pesticide plant in Bhopal on December 3, 1984.

Around 12 a.m. the plant released 40 tons of methyl isocyanate

(MIC) gas and other toxins, resulting in the exposure of over
500,000 people.
2. Bhopal – India
Bhopal - the World's Worst Industrial Disaster

Estimates vary on the death toll. The government has confirmed a

total of 4000 deaths related to the gas release.

Other government agencies estimate 15,000 deaths. Others estimate

8000 to 10,000 died within 72 hours and 25,000 have since died
from gas-related diseases.
2. Bhopal – India
Bhopal - the World's Worst Industrial Disaster

25 years after the gas leak, 390 tonnes of toxic chemicals

abandoned at the Union Carbide plant continue to leak and pollute
the groundwater.

There are currently civil and criminal cases related to the disaster
ongoing in the United States District Court, the District Court of
Bhopal, against Union Carbide, now owned by Dow Chemical
Company, with an Indian arrest warrant pending against Warren
Anderson, CEO of Union Carbide at the time of the disaster.
2. Bhopal – India
Lethal Dose Comparison
2. Bhopal – India
Bhopal Industrial Disaster
2. Bhopal – India
Bhopal Disaster
2. Bhopal – India
Areas affected by MIC release A vast stock of MIC provoked by ingress
of water unleashed a furious gas cloud on
unsuspecting people, at midnight “A
Sleeping community outside as the gas
began its spread. Bodies roused, coughing,
crying out, eyes burning and watering.
Thousands running, staggering through
alleys, many clutching their babies, not
knowing where to run, which way to
escape. Death by the thousands, injuries
by the tens of thousands. Pandemonium in
the hospital. By daybreak the scene of
silence around those left behind: Fathers,
mothers, children, cows, bulls, goats, dogs
– all in final repose. A peace in its eeriness
never before more heart wrenching. Mass
cremations, mass burials”. -Wil
Lepkowski, C & EN News,1985.
3. Seveso disaster, Italy
The Seveso disaster was an industrial accident that occurred on July
10, 1976, in a small chemical manufacturing plant (ICMESA) near
Milan in Italy. It resulted in the highest known exposure to 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD) in residential populations.
3. Seveso disaster, Italy

Trichlorophenol was intended as an intermediate for the herbicide

2,4,5-T (2,4,5-trichlorophenoxyacetic acid).

This reaction must be carried at a temperature above that of the

normal process utilities that were available, so the exhaust steam
from onsite the electricity turbine was passed around an external
heating coil of the reactor. The exhaust steam was at 12 bar and
190°C, resulting in a reaction mixture at 158°C.
3. Seveso disaster, Italy
The plant was supposed to shutdown over the weekend, and parts of
the site started to close down as batches finished. This caused the
load on the turbine to fall dramatically, resulting in the exhaust
steam temperature rising to around 300°C, heating the reactor wall
to the same temperature.

The relief valve eventually opened, and about 6 tonnes of chemicals

were released into the air. The accident was not immediately
noticed. No one was at the plant when it happened.
3. Seveso disaster, Italy

The first sign of health problems, burn-like skin lesions, appeared

on children a few hours after the accident. Latter a severe skin
disorder usually associated with dioxin, broke out on some of the
people most exposed to the cloud.

Authorities began an investigation five days after the accident,

when animals such as rabbits began to die en masse. Roughly
70,000 animals -- were killed to prevent contamination from
filtering up the food chain.
3. Seveso disaster, Italy

Image courtesy: Google Images

4. Pasadena, Texas
A massive explosion in Pasadena, Texas, on October 23, 1989,
resulted in 23 fatalities, 314 injuries, and capital losses of over $715
million.

This explosion occurred in a high-density polyethylene plant after

the accidental release of 85,000 pounds of a flammable mixture
containing ethylene, isobutane, hexane, and hydrogen.

The release formed a large gas cloud instantaneously because the

system was under high pressure and temperature.

The cloud was ignited about 2 minutes after the release by an

unidentified ignition source.
4. Pasadena, Texas
The damage resulting from the explosion made it impossible to
reconstruct the actual accident scenario.

However, evidence showed that the standard operating procedures

were not appropriately followed.

The release occurred in the polyethylene product takeoff system, as

illustrated in Figure1-12.

Usually the polyethylene particles (product) settle in the settling leg

and are removed through the product takeoff valve.

Occasionally, the product plugs the settling leg, and the plug is
removed by maintenance personnel.
4. Pasadena, Texas
4. Pasadena, Texas
The normal - and safe - procedure includes closing the DEMCO
valve, removing the air lines, and locking the valve in the closed
position.

Then the product takeoff valve is removed to give access to the

plugged leg.

The accident investigation evidence showed that this safe procedure

was not followed;

• specifically, the product takeoff valve was removed,

• the DEMCO valve was in the open position, and
• the lockout device was removed.
4. Pasadena, Texas
This scenario was a serious violation of well-established and
well-understood procedures and created the conditions that
permitted the release and subsequent explosion.

The OSHA investigation found that

(1) no process hazard analysis had been performed in the

polyethylene plant, and as a result, many serious safety
deficiencies were ignored or overlooked;

(2) the single-block (DEMCO) valve on the settling leg was not
designed to fail to a safe closed position when the air failed;

(3) rather than relying on a single-block valve, a double-

4. Pasadena, Texas

block-and-bleed valving arrangement or a blind flange after the

single-block valve should have
been used;

(4) no provision was made for the development, implementation,

and enforcement of effective permit systems (for example, line
opening); and

(5) no permanent combustible gas detection and alarm system was

located in the region of the reactors.
4. Pasadena, Texas
Other factors that contributed to the severity of this disaster were
also cited:

(1) Proximity of high-occupancy structures (control rooms) to

hazardous operation,

(2) inadequate separation between buildings, and

(3) crowded process equipment.

Major Oil Industry Accidents
Piper Alpha disaster.
July 6, 1988: An explosion and resulting fire on a North Sea oil
production platform.

Total insured loss is about US$ 3.4 billion. Rated as the world's
worst offshore oil disaster in terms both of lives lost and impact to
industry.

167 men were confirmed dead.

Major Oil Industry Accidents

Texas City Refinery explosion

March 23, 2005: An explosion occurred at a British Petroleum
refinery in Texas.

It is the third largest refinery in the United States and one of the
largest in the world, processing 433,000 barrels of crude oil per day
and accounting for 3% of that nation's gasoline supply.

Over 100 were injured, and 15 were confirmed dead.

Several level indicators failed, leading to overfilling of a drum, and

light hydrocarbons concentrated at ground level throughout the area.
A nearby running diesel truck set off the explosion.
Major Oil Industry Accidents

Hertfordshire Oil Storage Terminal fire

December 11, 2005:

A series of explosions at the Buncefield oil storage depot, described

as the largest peacetime explosion in Europe, devastated the terminal
and many surrounding properties.

There were no fatalities. Total damages have been forecast as £750

million.
Major Oil Industry Accidents

The Deepwater Horizon oil spill (BP oil spill)

April 20, 2010: in the Gulf of Mexico flowed for three months.

It is the largest accidental marine oil spill in the history of the

petroleum industry.

The explosion killed 11 men working on the platform and injured 17

others. About 4.9 million barrels of crude oil was released into the
sea.
Major Oil Industry Accidents

The Deepwater Horizon oil spill (BP oil spill)

Safety
The End