Role of Safety

industries

in

chemical

process

What is a Chemical Processing Industry ?

An industry in which the raw materials undergo chemical conversion during
their processing into finished products, as well as (or instead of) the physical
conversions common to industry in general; includes the traditional chemical,
petroleum,
and
petrochemical
industries.
The Chemical Processing Industry encompasses a broad range of products,
including petrochemical and inorganic chemicals, plastics, detergents, paints
and pigments, and more.
Major segments of our Chemical Processing include:

Inorganic and Organic Chemical Producers

Producers of olefins, alcohols, ethylene and ethylene-based chemicals,
polymerization, cyclical compounds, and solvents. Major companies engaged in
the production of acids, compounds, and specialty chemicals

Industrial Gas Producers

Manufacturers of hydrogen, nitrogen, oxygen, and other industrial gases

Agricultural Chemical Industry

Bulk liquid and solid (granular, powder) agricultural product producers,
including fertilizers, herbicides, pesticides, fungicides, and intermediates, such
as urea, ammonia, nitric acid, and ammonium nitrate

Detergents and other Household Product Producers

Manufacturers of soaps and detergents, cleaners, bleaches, disinfectants, and
surface agents

Plastics, Rubbers, Fibers, and Resins Manufacturers

The manufacturing of synthetic resins, plastics materials, nonvulcanizable

elastomers, synthetic rubber by polymerization or copolymerization, cellulosic
man-made fibers and the compounding of purchased plastics

Painting and Coating Producers

Manufacturers of pigments, coatings, solvents, lacquers, enamels, stains, and
varnishes for finishing

Producers of Other Chemicals

Producers of explosives to inks, dyes, glues, lubricants, fire retardants, and
chemical preparations

Alkalies and Chlorine

Producers of caustic soda, soda ash (not produced at mines), chlorine
(compressed or liquefied), carbonates (potassium and sodium)

The Nature of the Accident Process

Chemical plant accidents follow typical patterns. It is important to study these
patterns in order to anticipate the types of accidents that will occur. As shown in
Table 1-6, fires are the most common, followed by explosion and toxic release.
With respect to fatalities, the order reverses ,with toxic release having the
greatest potential for fatalities.Economic loss is consistently high for accidents
involving explosions. The most damaging type of explosion is an unconfined
vapor cloud explosion, where a large cloud of volatile and flammable vapor is
released and dispersed throughout the plant site followed by ignition and
explosion of the cloud. An analysis of the largest chemical plant accidents(based
on worldwide accidents and 1998 dollars) is provided in Figure 1-6. As
illustrated, vapor cloud explosions account for the largest percentage of these
large losses.The other category of Figure 1-6 includeslosses resulting from
floods and windstorms.Toxic release typically results in little damage to capital
equipment. Personnel injuries,employee losses, legal compensation, and
cleanup liabilities can be significant.

The Nature of the Accident Process

Fires
Others
Explosions
Vapour cloud
explosions

Figure Types of loss for large hydrocarbon chemical plant accidents

Figure 1-7 presents the causes of losses for the largest chemical accidents. By
far the largest cause of loss in a chemical plant is due to mechanical
failure.Failures of this type areusually due to a problem with maintenance.
Pumps, valves, and control equipment will fail ifnot properly maintained. The
second largest cause is operator error. For example, valves arenot opened or
closed in the proper sequence or reactants are not charged to a reactor in the
correct order. Process upsets caused by, for example, power or cooling water
failures account for 11% of the losses. Human error is frequently used to
describe a cause of losses. Almost all accidents, except those caused by natural
hazards, can be attributed to human error. For instance, mechanical failures
could all be due to human error as a result of improper maintenance or
inspection.

Accidents %
45
40
35
30
25
20
15
10
5
0

Figure 1-7 Causes of losses in the largest hydrocarbon-chemical plant accidents.

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)

Inherent Safety
An inherently safe plant11,12 relies on chemistry and physics
to prevent accidents rather than on control systems, interlocks,
redundancy, and special operating procedures to prevent
accidents. Inherently safer plants are tolerant of errors and are
often the most cost effective. 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. In general, the
safety of a process relies on multiple layers 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. Inherent safety is a part of all
layers of protection; however, it is especially directed toward
process design features. The best approach to prevent
accidents is to add process design features to prevent
hazardous situations. An inherently safer plant is more tolerant
of operator errors and abnormal conditions. Although a process
or plant can be modified to increase inherent safety at any time
in its life cycle, the potential for major improvements is the
greatest at the earliest stages of process development. At
these early stages process engineers and chemists have the
maximum degree of freedom in the plant and process
specifications, and they are free to consider basic process
alternatives, such as changes to the fundamental chemistry
and technology. The major approach to inherently safer process
designs is divided into the following
categories:
intensification
substitution
attenuation
limitation of effects
simplification/error tolerance

Inherent Safety Techniques

Type

Typical techniques

Minimize

Change from large batch reactor to a smaller continuous

reactor
Reduce storage inventory of raw materials
Improve control to reduce inventory of hazardous
intermediate chemicals
Reduce process hold-up
Use mechanical pump seals vs. packing
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

Substitute

Moderate

Simplify

properties
Use water as a heat transfer fluid instead of hot oil
Use vacuum to reduce boiling point
Reduce process temperatures and pressures
Refrigerate storage vessels
Dissolve hazardous material 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
Keep piping systems neat and visually easy to follow
Design control panels that are easy to comprehend
Design plants for easy and safe maintenance
Pick equipment that requires less maintenance
Pick equipment with low failure rates
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 vessels and controls to enhance understanding

Vapor released from spills can be minimized by designing dikes so that

flammable and toxic materials will not accumulate around leaking tanks.
Smaller tanks also reduce the hazards of a release. While minimization
possibilities are being investigated, substitutions should also be considered as an
alternative or companion concept; that is, safer materials should be used in
place of hazardous ones. This can be accomplished by using alternative
chemistry that allows the use of less hazardous materials or less severe
processing conditions. When possible, toxic or flammable solvents should be
replaced with less hazardous solvents (for example,water-based paints and
adhesives and aqueous or dry flowable formulations for agricultural chemicals).
Another alternative to substitution is moderation, that is, using a hazardous
material under less hazardous conditions. Less hazardous conditions or less
hazardous forms of a material include (1) diluting to a lower vapor pressure to
reduce the release concentration, (2) refrigerating to lower the vapor pressure,
(3) handling larger particle size solids to minimize dust, and (4) processing
under less severe temperature or pressure conditions. Containment buildings are

sometimes used to moderate the impact of a spill of an especially toxic material.

When containment is used, special precautions are included to ensure worker
protection, such as remote controls, continuous monitoring, and restricted
access. Simpler plants are friendlier than complex plants because they provide
fewer opportunities for error and because they contain less equipment that can
cause problems. Often, the reason for complexity in a plant is the need to add
equipment and automation to control the hazards. Simplification reduces the
opportunities for errors and misoperation. For example, (1) piping systems can
be designed to minimize leaks or failures, (2) transfer systems can be designed
to minimize the potential for leaks, (3) process steps and units can be separated
to prevent the domino effect, (4) fail-safe valves can be added, (5) equipment
and controls can be placed in a logical order, and (6) the status of the process
can be made visible and clear at all times. The design of an inherently safe and
simple piping system includes minimizing the use of sight glasses, flexible
connectors, and bellows, usingwelded pipes for flammable and toxic chemicals
and avoiding the use of threaded pipe, using spiral wound gaskets and flexible
graphitetype gaskets that are less prone to catastrophic failures, and using
proper support of lines to minimize stress and subsequent failures.

Occupational safety and health protection and chemical industry

enterprises
Chemical industry enterprises are aware of the fact that they are monitored and
evaluated by the state authorities, business partners, the public and also by their
staff members according to how they care for occupational safety and health
protection. Their long-term approach to this area is characterized by high
responsibility, with emphasis laid on prevention and primarily on minimizing
risks to the health and life of employees. Already in 1985 a worldwide voluntary
programme Responsible Care (hereinafter RC) was launched in Canada, whose
aim is to reduce risks related with chemical production processes and to openly
communicate with the state administration bodies and the public about
approaches to chemical industry safety improvements.
Very intensive attention to the occupational safety and health protection issues
is paid at the level of European Chemical Industry Council (CEFIC). With
regard to high importance of these issues, in the past a number of European
chemical industry enterprises and institutions published more or less extensive
reports on approaches to occupational safety and health protection and on the
progress of performance in this area. The chosen indicators were differing
Human Resources Management & Ergonomics 2/2008
from enterprise to enterprise and from state to state, in
dependence on national and local priorities and definitions. For
this reason, in 1998 CEFIC prepared a new document
Responsible Care, Health, Safety and Environmental Reporting

Guidelines, which forms a common framework for the

reporting of results and monitoring and allows to summarize
the data at European level, as all member federations in
publishing the data follow common basic parameters and their
definitions. Results of the European chemical industry are
published in regular reports that are released by CEFIC. The
data displayed cover more than 895 000 employees of the
European chemical industry.

Are there any differences in approach to

occupational health and safety management in small
and large chemical businesses?
At the beginning of 2008, research in two selected Czech chemical industry
enterprises (with place of business on the territory of the Pardubice Region) was
conducted, having focused on identifying the approach of these enterprises to
occupational safety and health protection issues. Of concern were, in particular,
occupational health and safety management and the matter of informing the
interested parties of corporate approach to these issues. Within health and safety
management, attention was primarily paid to the following aspects:
- The importance of occupational health and safety management.
- Reasons for implementation or non-implementation of HSMS.
- Assistance in implementation of HSMS.
- Problems in implementation and system benefits.
- Occupational risk assessment, the provision of personal protective aids.
- Regular health and safety inspections, trainings and health and safety
documentation.
Within the reporting, particularly the following areas were examined:
- Making the information available to the public through regular reports, the
reasons for preparing such reports, the way of reporting.
- Interest in information.
The research was conducted in a small and in a large chemical business. The
small business is specialized in dyeing and refining of plastics; the main
corporate operations include the manufacture of chemical substances and
chemical preparations, wholesale and retail of chemicals. The business has been
in existence since 1950 and has approx. 40 employees. The large business is a
leading European manufacturer of sophisticated chemical products with more
than eighty years tradition and employs over 2 200 staff members. It

manufactures more than 1000 products and exports to 54 countries worldwide.

Business activities are targeted at three market segments: advanced organic
intermediates, cellulose derivatives, and pigments and dyes.
The research was conducted in the form of in-depth interview. In the small
business, interview proceeded with applications engineer who has been working
in the firm for a number of years and the inquired areas fall within his
competence. In the large business, discussion (with regard to much broader
differentiation of competences) proceeded with two staff members who are
engaged in these issues, namely head of occupational safety department and
staff manager of the company.
In the area of occupational health and safety management, the following
findings were identified .
a) For a small business, improvements in occupational safety and health
protection are very important. The business has its HSMS implemented since
1999; this system is not certified. Implementation of the system was suggested
by company management, mainly driven by efforts to achieve higher level of
occupational safety and avoid the occurrence of occupational injuries. The need
to build up the system also resulted from the requirements of business partners.
In the process of the system implementation, assistance from external subjects
(safety engineer and adviser) was made use of. Occupational risk assessment
together with assessment of risks for the provision of personal protective aids as
well as operational risk assessment was carried out. Technological procedures,
given by Labour Code, have been elaborated. Based on this, measures aiming to
minimize and/or eliminate the risks have been adopted. The business ensures
safe condition of the technical equipment and facilities through maintenance
and regular checks and revisions, it has also first aid system for the sake of
accidents and breakdowns (a so-called traumatology and evacuation plan which
forms part of occupational health and safety documentation) elaborated. The
business performs regular trainings of staff members and managers in the
occupational health and safety issues. It also performs entry trainings in the
occupational health and safety issues that are provided by safety engineer and
recorded in every employees file. Preventive checks on occupational health and
safety are performed by contract physician. The business also performs checks
on its staff members whether they are not intoxicated. From the listed activities
it is evident that the main aim of the system is to achieve compliance with the
legislation.
b) The large business has an occupational health and safety management system
implemented and strives for the certification according to the guideline OHSAS
18001:1999 (Occupation Health and Safety Management Systems). The main
reasons for implementation of the system include efforts to achieve higher level
of occupational safety, efforts to achieve a lower number of occupational
accidents and injuries and reduce costs resulting from compensations for

occupational accidents and injuries. Implementation of the system was

suggested directly by corporate management, having been performed by
company itself, unassisted. Within this system, emphasis is primarily laid on
making company staff members acquainted with the risks resulting from the
nature of production, namely through initial training in the form of educational
film and assisting materials prepared by occupational safety department.
Permanent attention is paid by enterprise to the trainings and periodical
examinations of skills and qualifications of employees who for performance of
their work must have special professional qualifications, prescribed by generally
valid legislation (autotruck drivers, gas facilities operating staff, welders,
scaffolders, etc.). The company ensures regular checks on occupational health
and safety as well as prescribed revisions to be performed by engineering
inspector, and also provides employees with personal protective aids. The
company has first aid system elaborated for the sake of accidents and
breakdowns, and strives to continuously update the system. The company
cooperates with 5 contract physicians who perform regular preventive
examinations and it is also in permanent contact with the regional hospital and
with the regional hygiene station. The company has put into operation alert
system which through SMS informs of danger the population living in the
surroundings. Corporate principles regarding the occurrence of
impaired/intoxicated individuals are followed very strictly, for that purpose,
spot checks are performed at the building entrance. The business keeps
occupational health and safety documentation (book of accidents, records of
occupational accidents and records of personal protective aids). To reach
compliance with the legal regulations, the business implemented HSMS and
strives for its certification. The business also uses another voluntary tool it
professes the RC principles and is a holder of the RC logo.
As regards the area of reporting, the following can be stated:
a) Small business makes available to the public the basic information on its
activities in the field of environmental protection and on work law relations
this is included in annual report; such obligation ensues from the Accounting
Act. Annual report is compiled every year as of 31.12. It is available to the
general public. It is made available on the intranet and also in printed form.
b) Factual and full disclosure of information on corporate activities in the area
of environmental protection and protection of working environment has become
a matter of course for a large business. The main aim in this area is the maximal
openness towards the employees and all other partners, such as the public,
public media, public administration, non-governmental organizations and
business partners. The main corporate targets in the area of environmental
protection and occupational safety and health protection as well as the way of
achieving them are presented by the business in regularly released Reports on
Corporate Environmental Impacts. The reports are distributed in printed form
and are also available to the public on corporate website. The business is a

holder of RC logo and based on its participation in this programme it also meets
all obligations in the area of disclosure of information. In addition, the basic
information on corporate environmental approach and on work law relations is
included in annual report. Annual report is placed on corporate website and is
also available in the form of CD version. The business regularly organizes
meetings with mayors of the municipalities in the region, where the participants
are made acquainted with various activities not only in the area of
environmental protection but also in the area of occupational safety and health
protection. Up-to-date information is also made available to the public by means
of corporate periodical. From the listed activities in the area of communication
with the interested parties it is evident that the business goes above the
framework of legal requirements. This means that it is aware of the importance
of communication for improving credibility of the company and its
attractiveness as employer. To address the interested parties, the business also
chooses different communication tools. Such communication activity is also,
beyond all doubt, a response to the requirements of the interested parties.

Safety Through Design in the Chemical Process

Industry:
Inherently Safer Process Design
A chemical manufacturing process is described as inherently safer if it
reduces or eliminates hazards associated with materials and operations used in
the process, and this reduction or elimination is a permanent and inseparable
part of the process technology. A hazard is defined as a physical or chemical
characteristic that has the potential for causing harm to people, the environment,
or property (adapted from CCPS, 1992). The key to this definition is that the
hazard is intrinsic to the material, or to its conditions of storage or use. For
example, chlorine is toxic by inhalation, gasoline is flammable, and steam at
600 psig contains significant potential energy. These hazards are basic
properties of the materials and the conditions of usage, and cannot be changed.
An inherently safer process reduces or eliminates the hazard by reducing the
quantity of hazardous material or energy, or by completely eliminating the
hazardous agent. A traditional approach to managing the risk associated with a
chemical process is by providing layers of protection between the hazardous
agent and the people, environment, or property which is potentially impacted.
This approach is illustrated in Figure 1 (CCPS, 1993b; Bollinger, et. al., 1996).
The protective layers may include one or more of the following:
The process design

 Basic controls, alarms, and operator control

Critical alarms, operator control, and manual intervention
Automatic actions emergency shutdown systems and safety interlock
systems
Physical protection equipment such as pressure relief devices
Physical mitigation systems such as spill containment dikes
Emergency response systems for example, fire fighting
Community emergency response for example, notification and evacuation
The layers of protection are intended to reduce risk by reducing either the
likelihood of potential incidents resulting in an impact on people, the
environment, or property, or by reducing the magnitude of the impact should an
incident occur. The risk can be reduced to very low levels by providing a
sufficient number of layers of protection, and by making each layer highly
reliable (Figure 2). However, the basic process hazards remain, and there is
always the potential perhaps very small, but never zero that all layers will
fail simultaneously and the hazardous incident will occur. Furthermore, the
layers of protection require significant expenditure of resources, both to design
and build them initially, and to maintain their reliability throughout the life of
the plant. Failure to adequately maintain the layers of protection may result in a
significant increase in the process risk .
The inherently safer design approach is to eliminate or reduce the hazard by
changing the process itself, rather than by adding on additional safety devices
and layers of protection. Ideally, hazards would be reduced to a level where no
protective systems are required because the hazard is too small to be of concern
Even if this is not possible, an inherently safer process will allow the number
of layers of protection to be reduced. The overall design is therefore more
robust from a safety and environmental viewpoint, and is likely to be less
expensive to build and operate because of the elimination of complex safety
systems.

Relatio

nship to Safety in Design

Safety in Design can be based on either of the approaches described. Add-on
safety features and layers of protection can be identified and incorporated
during design. In fact, they should be incorporated into the process design
we should anticipate potential accidents during design and provide the
appropriate protective systems, procedures, and devices, rather than discovering
the need for these layers of protection later on as a result of accidents and near
misses. However, the greatest potential for realizing an inherently safer process
design is early in development. At this time, the designer still has considerable
freedom in technology selection. For a chemical process, perhaps the greatest
opportunities lie in the selection of the chemical synthesis route to be used,
including the raw materials, solvents, chemical intermediates, reaction steps,
and other physical and chemical operations to be used.

However, it is important to remember that it is never too late to consider

inherently safer design options. In an existing plant, there will be different kinds
of opportunities for modifications to improve inherent safety, but these
opportunities can result in significant improvements. It may not be feasible to
change the basic process chemistry and technology, but it may be possible to
reduce inventory, simplify the plant, or otherwise make the plant more user
friendly. Significant improvements in the inherent safety of plants which have
operated for many years have been reported.

Approaches to Inherently Safer Design in the

Chemical Industry
Chemical process risk management approaches can be classified into four
categories:
Inherent Eliminating the hazard by using materials and process conditions
which are non-hazardous.
Passive Minimizing the hazard by process and equipment design features
which reduce either the frequency or consequence of the hazard without the
active functioning of any device.
Active Using controls, safety interlocks, and emergency shutdown systems
to detect and correct process deviations. These systems are commonly referred
to as engineering controls.
Procedural Using operating procedures, administrative checks, emergency
response, and other management approaches to prevent incidents, or to
minimize the effects of an incident.
Marshall (1990) categorizes risk management strategies as strategic and tactical.
Strategic approaches include measures which have wide significance, and
which represent a once and for all policy decision. Inherent and passive
approaches tend to fall into the strategic category. Tactical approaches include
measures which are added on at a late state or those which entail frequent
repetition. Active controls and procedural approaches tend to be tactical.
Safety in Design can entail both strategic and tactical risk management
approaches, but the greatest benefits are realized from the early consideration of
strategic risk management measures. There are four basic strategies for
implementing inherently safer chemical processes:
Minimize Use smaller quantities of hazardous substances
Continuous reactors (stirred tanks, loop reactors, tubular reactors) in place of
batch
reactors
Reduced inventory of raw materials and in-process intermediates
High efficiency heat exchangers
Example: A 50-liter loop polymerization reactor has a capacity equal to that of
a 5000liter batch reactor (Wilkinson and Geddes, 1993).
Substitute Replace a material with a less hazardous substance
Water based paints and coatings
Alternative chemistry using less hazardous materials

Less flammable or toxic solvents

Example: Acrylic esters were formerly manufactured using the Reppe process,
using
acetylene, carbon monoxide, and a nickel carbonyl catalyst. The newer
propylene oxidation
process uses significantly less hazardous materials (Hochheiser, 1986).
Moderate Use less hazardous conditions, a less hazardous form of a
material, or
facilities which minimize the impact of a release of hazardous material or
energy
Dilution
Refrigeration of volatile hazardous materials
Granular agricultural product formulations in place of powders
Example: The distance to an atmospheric concentration of 500 ppm of monomethylamine in the event of the failure of a 2-inch pipe is reduced from 1.9
miles to 0.6 miles by reducing the temperature of the monomethylamine from
10C to -6C .
Simplify Design facilities which eliminate unnecessary complexity and
make operating errors less likely, and which are forgiving of errors which are
made
Develop fundamentally simpler technology with fewer reactions and
processing operations
Eliminate unnecessary equipment (question need for each device or feature)
Remove unused or abandoned equipment
Human factors considerations in design
Example: Design vessels to withstand the maximum pressure which can be
generated, rather than providing complex emergency relief systems, including
devices such as scrubbers, catch tanks, or flares to contain the relief system
effluent.

CASE STUDIES
Four Significant Disasters
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) are

presented here. All these accidents had a significant impact on
public perceptions and the chemical engineering profession
that added new emphasis and standards in
the practice of safety. Chapter 13 presents case histories in
considerably more detail. The Flixborough accident is perhaps
the most documented chemical plant disaster. The British
government insisted on an extensive investigation.

Flixborough, England
The accident at Flixborough, England, occurred on a Saturday in June 1974.
Although it was not reported to any great extent in the United States, it had a
major impact on chemical engineering in the United Kingdom. As a result of the
accident, safety achieved a much higher priority in that country.
The Flixborough Works of Nypro Limited was designed to produce 70,000 tons
per year of caprolactam, a basic raw material for the production of nylon. The
process uses cyclohexane, which has properties similar to gasoline. Under the
process conditions in use at Flixborough (155C and 7.9 atm), the cyclohexane
volatilizes immediately when depressurized to atmospheric conditions.
The process where the accident occurred consisted of six reactors in series. In
these reactors cyclohexane was oxidized to cyclohexanone and then to
cyclohexanol using injected air in the presence of a catalyst. The liquid reaction
mass was gravity-fed through the series of reactors. Each reactor normally
contained about 20 tons of cyclohexane. Several months before the accident
occurred, reactor 5 in the series was found to be leaking. Inspection showed a
vertical crack in its stainless steel structure. The decision was made to remove
the reactor for repairs. An additional decision was made to continue operating
by connecting reactor 4 directly to reactor 6 in the series. The loss of the reactor
would reduce the yield but would enable continued production because
unreacted cyclohexane is separated and recycled at a later stage.
The feed pipes connecting the reactors were 28 inches in diameter. Because
only 20-inch pipe stock was available at the plant, the connections to reactor 4
and reactor 6 were made using flexible bellows-type piping, as shown in Figure
1-10. It is hypothesized that the bypass pipe section ruptured because of
inadequate support and overflexing of the pipe section as a result of internal
reactor pressures. Upon rupture of the bypass, an estimated 30 tons of
cyclohexane volatilized and formed a large vapor cloud. The cloud was ignited
by an unknown source an estimated 45 seconds after the release.
The resulting explosion leveled the entire plant facility, including the
administrative offices. Twenty-eight people died, and 36 others were injured.
Eighteen of these fatalities occurred in the main control room when the ceiling

collapsed. Loss of life would have been substantially greater had the accident
occurred on a weekday when the administrative offices were filled with
employees. Damage extended to 1821 nearby houses and 167 shops and
factories. Fifty-three civilianswere reported injured. The resulting fire in the
plant burned for over 10 days. This accident could have been prevented by
following proper safety procedures.

Bhopal, India
The Bhopal, India, accident, on December 3, 1984, has received
considerably more attention than the Flixborough accident. This
is due to the more than 2000 civilian casualties that resulted.
The Bhopal plant is in the state of Madhya Pradesh in central
India. The plant was partially owned by Union Carbide and
partially owned locally. The nearest civilian inhabitants were 1.5
miles away when the plant was constructed. Because the plant
was the dominant source of employment in the area, a
shantytown eventually grew around the immediate area. The
plant produced pesticides. An intermediate compound in this
process is methyl isocyanate (MIC). MIC is an extremely
dangerous compound. It is reactive, toxic, volatile, and
flammable. The maximum exposure concentration of MIC for
workers over an 8-hour period is 0.02 ppm (parts per million).
Individuals exposed to concentrations of MIC vapors above 21
ppm experience severe irritation of the nose and throat. Death
at large concentrations of vapor
is due to respiratory distress. MIC demonstrates a number of
dangerous physical properties. Its boiling point at atmospheric
conditions is 39.1C, and it has a vapor pressure of 348mmHgat
20C.Thevapor is about twice as heavy as air, ensuring that the
vapors will stay close to the ground once released. MICreacts
exothermicallywithwater.Although the reaction rate is slow, with
inadequate cooling the temperature will increase and the MIC
will boil. MIC storage tanks are typically refrigerated to prevent
this problem. The unit using the MIC was not operating because
of a local labor dispute. Somehow a storage tank containing a
large amount of MIC became contaminated with water or some
other substance.Achemical reaction heated theMIC to a
temperature past its boiling point. TheMIC vapors traveled
through a pressure relief system and into a scrubber and flare
system installed to consume theMICin the event of a
release.Unfortunately, the scrubber and flare systemswere not

operating, for a variety of reasons. An estimated 25 tons of

toxic MIC vapor was released. The toxic cloud spread to the
adjacent town, killing over 2000 civilians and injuring an
estimated 20,000 more. No plant workers were injured or killed.
No plant equipment was damaged. The exact cause of the
contamination of the MIC is not known. If the accident was
caused by a problem with the process, a well-executed safety
review could have identified the problem. The scrubber and
flare system should have been fully operational to prevent the
release. Inventories of dangerous chemicals, particularly
intermediates, should also have been minimized. The reaction
includes the dangerous intermediate MIC. An alternative
reaction scheme is shown at the bottom of the figure and
involves a less dangerous chloroformate intermediate. Another
solution is to redesign the process to reduce the inventory of
hazardous MIC. One such design produces and consumes the
MIC in a highly localized area of the process, with an inventory
of MIC of less than 20 pounds.

Seveso, Italy
Seveso is a small town of approximately 17,000 inhabitants, 15
miles from Milan, Italy. The plant was owned by the Icmesa
Chemical Company. The product was hexachlorophene, a
bactericide, with trichlorophenol produced as an intermediate.
During normal operation, a small amount of TCDD (2,3,7,8tetrachlorodibenzoparadioxin) is produced in the reactor as an
undesirable side-product. TCDD is perhaps the most potent
toxin known to humans. Animal studies have shown TCDD to be
fatal in doses as small as 10_9 times the body weight. Because
TCDD is also insoluble in water, decontamination is difficult.
Nonlethal doses of TCDD result in chloracne, an acne-like
disease that can persist for several years. On July 10, 1976, the
trichlorophenol reactor went out of control, resulting in a higher
than normal operating temperature and increased production of
TCDD. An estimated 2 kg of TCDD was released through a relief
system in a white cloud over Seveso. A subsequent heavy
rain washed the TCDD into the soil. Approximately 10 square
miles were contaminated. Because of poor communications
with local authorities, civilian evacuation was not started until
several days later. By then, over 250 cases of chloracne were
reported. Over 600 people were evacuated, and an additional

2000 people were given blood tests. The most severely

contaminated area immediately adjacent to the plant was
fenced, the condition it remains
in today. TCDD is so toxic and persistent that for a smaller but
similar release of TCDD in Duphar, India, in 1963 the plant was
finally disassembled brick by brick, encased in concrete and
dumped into the ocean. Less than 200 g of TCDD was released,
and the contamination was confined to the plant. Of the 50
men assigned to clean up the release, 4 eventually died from
the exposure.
The Seveso and Duphar accidents could have been avoided if
proper containment systems had been used to contain the
reactor releases. The proper application of fundamental
engineering safety principles would have prevented the two
accidents. First, by following proper procedures, the initiation
steps would not have occurred. Second, by using proper hazard
evaluation procedures, the hazards could have been identified
and corrected before the accidents occurred.

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. 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.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 13Occupational
Safety and Health Administration is removed by maintenance

personnel. The normaland safeprocedure 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
procedurewas not followed; specifically, the product takeoff
valvewas removed, the DEMCO valvewas in the open position,
and the lockout device was removed. This scenario was a
serious violation of well-established and well-understood
procedures and created the conditions that permitted the
release and subsequent
explosion.
TheOSHAinvestigation13 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
legwas not designed to fail to a safe closed position when the
air failed; (3) rather than relying on a single-block valve a doubleblock-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. 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.