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.

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

Subsequent layers include control systems. interlocks. and special operating procedures to prevent accidents. operated at less severe temperatures and pressures.Accidents % 45 40 35 30 25 20 15 10 5 0 Figure 1-7 Causes of losses in the largest hydrocarbon-chemical plant accidents. In general. A process that does not require complex safety interlocks and elaborate procedures is simpler. and • termination (the event or events that stop the accident or diminish it in size) Inherent Safety An inherently safe plant11. Inherently safer plants are tolerant of errors and are often the most cost effective. easier to operate. 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). interlocks. . has lower capital and operating costs. Smaller equipment. the safety of a process relies on multiple layers of protection.12 relies on chemistry and physics to prevent accidents rather than on control systems. The first layer of protection is the process design features. redundancy. and more reliable.

and other less hazardous Substitute . it is especially directed toward process design features. packing Use welded pipe vs. and they are free to consider basic process alternatives. An inherently safer plant is more tolerant of operator errors and abnormal conditions. 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. flanged Use solvents that are less toxic Use mechanical gauges vs. At these early stages process engineers and chemists have the maximum degree of freedom in the plant and process specifications. Inherent safety is a part of all layers of protection. The best approach to prevent accidents is to add process design features to prevent hazardous situations. and emergency response plans. alarms. however. mercury Use chemicals with higher flash points. Although a process or plant can be modified to increase inherent safety at any time in its life cycle. boiling points.safety shutdown systems. the potential for major improvements is the greatest at the earliest stages of process development. protective systems.

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. Containment buildings are . (2) refrigerating to lower the vapor pressure. and (4) processing under less severe temperature or pressure conditions. that is. Smaller tanks also reduce the hazards of a release.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. Another alternative to substitution is moderation. (3) handling larger particle size solids to minimize dust. substitutions should also be considered as an alternative or companion concept. While minimization possibilities are being investigated. When possible. toxic or flammable solvents should be replaced with less hazardous solvents (for example. safer materials should be used in place of hazardous ones. 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.water-based paints and adhesives and aqueous or dry flowable formulations for agricultural chemicals). This can be accomplished by using alternative chemistry that allows the use of less hazardous materials or less severe processing conditions.

(3) process steps and units can be separated to prevent the domino effect. When containment is used. Safety and Environmental Reporting . (5) equipment and controls can be placed in a logical order. in 1998 CEFIC prepared a new document „Responsible Care. using spiral wound gaskets and flexible graphitetype gaskets that are less prone to catastrophic failures. with emphasis laid on prevention and primarily on minimizing risks to the health and life of employees. For this reason. With regard to high importance of these issues. the reason for complexity in a plant is the need to add equipment and automation to control the hazards. and bellows. Their long-term approach to this area is characterized by high responsibility. (2) transfer systems can be designed to minimize the potential for leaks. 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. 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. Already in 1985 a worldwide voluntary programme Responsible Care (hereinafter RC) was launched in Canada. 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. Very intensive attention to the occupational safety and health protection issues is paid at the level of European Chemical Industry Council (CEFIC). (1) piping systems can be designed to minimize leaks or failures. Simplification reduces the opportunities for errors and misoperation. the public and also by their staff members according to how they care for occupational safety and health protection. (4) fail-safe valves can be added. usingwelded pipes for flammable and toxic chemicals and avoiding the use of threaded pipe. Health. in dependence on national and local priorities and definitions. special precautions are included to ensure worker protection. flexible connectors. For example. and restricted access. Often. Simpler plants are friendlier than complex plants because they provide fewer opportunities for error and because they contain less equipment that can cause problems. and (6) the status of the process can be made visible and clear at all times. and using proper support of lines to minimize stress and subsequent failures.sometimes used to moderate the impact of a spill of an especially toxic material. such as remote controls. business partners. continuous monitoring. The chosen indicators were differing Human Resources Management & Ergonomics 2/2008 from enterprise to enterprise and from state to state. The design of an inherently safe and simple piping system includes minimizing the use of sight glasses.

Problems in implementation and system benefits.Interest in information.Reasons for implementation or non-implementation of HSMS. the way of reporting. .Assistance in implementation of HSMS. Of concern were. The data displayed cover more than 895 000 employees of the European chemical industry. Results of the European chemical industry are published in regular reports that are released by CEFIC. The research was conducted in a small and in a large chemical business.Guidelines“. . having focused on identifying the approach of these enterprises to occupational safety and health protection issues. in particular. The business has been in existence since 1950 and has approx. research in two selected Czech chemical industry enterprises (with place of business on the territory of the Pardubice Region) was conducted. attention was primarily paid to the following aspects: .Regular health and safety inspections.Making the information available to the public through regular reports. 40 employees. which forms a common framework for the reporting of results and monitoring and allows to summarize the data at European level. Are there any differences in approach to occupational health and safety management in small and large chemical businesses? At the beginning of 2008. The small business is specialized in dyeing and refining of plastics. the reasons for preparing such reports. particularly the following areas were examined: .Occupational risk assessment. trainings and health and safety documentation.The importance of occupational health and safety management. . as all member federations in publishing the data follow common basic parameters and their definitions. It . the provision of personal protective aids. occupational health and safety management and the matter of informing the interested parties of corporate approach to these issues. Within the reporting. Within health and safety management. . the main corporate operations include the manufacture of chemical substances and chemical preparations. wholesale and retail of chemicals. . 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. .

efforts to achieve a lower number of occupational accidents and injuries and reduce costs resulting from compensations for .manufactures more than 1000 products and exports to 54 countries worldwide. the following findings were identified . and pigments and dyes. 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. Occupational risk assessment together with assessment of risks for the provision of personal protective aids as well as operational risk assessment was carried out. cellulose derivatives. 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. Based on this. The business also performs checks on its staff members whether they are not intoxicated. this system is not certified. From the listed activities it is evident that the main aim of the system is to achieve compliance with the legislation. measures aiming to minimize and/or eliminate the risks have been adopted. discussion (with regard to much broader differentiation of competences) proceeded with two staff members who are engaged in these issues. Technological procedures. The need to build up the system also resulted from the requirements of business partners. have been elaborated. given by Labour Code. The business performs regular trainings of staff members and managers in the occupational health and safety issues. 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). a) For a small business. mainly driven by efforts to achieve higher level of occupational safety and avoid the occurrence of occupational injuries. The business has its HSMS implemented since 1999. In the small business. In the large business. The main reasons for implementation of the system include efforts to achieve higher level of occupational safety. assistance from external subjects (safety engineer and adviser) was made use of. The business ensures safe condition of the technical equipment and facilities through maintenance and regular checks and revisions. In the process of the system implementation. Implementation of the system was suggested by company management. In the area of occupational health and safety management. The research was conducted in the form of in-depth interview. It also performs entry trainings in the occupational health and safety issues that are provided by safety engineer and recorded in every employee’s file. Preventive checks on occupational health and safety are performed by contract physician. namely head of occupational safety department and staff manager of the company. improvements in occupational safety and health protection are very important. Business activities are targeted at three market segments: advanced organic intermediates.

scaffolders. such obligation ensues from the Accounting Act. the business implemented HSMS and strives for its certification. The reports are distributed in printed form and are also available to the public on corporate website. 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. It is made available on the intranet and also in printed form. The business also uses another voluntary tool – it professes the RC principles and is a holder of the RC logo. Implementation of the system was suggested directly by corporate management. The business keeps occupational health and safety documentation (book of accidents. The company has first aid system elaborated for the sake of accidents and breakdowns. non-governmental organizations and business partners. 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. emphasis is primarily laid on making company staff members acquainted with the risks resulting from the nature of production. such as the public. The main aim in this area is the maximal openness towards the employees and all other partners. Corporate principles regarding the occurrence of impaired/intoxicated individuals are followed very strictly. 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. welders. The business is a . It is available to the general public. The company has put into operation alert system which through SMS informs of danger the population living in the surroundings. 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 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. public administration. for that purpose. As regards the area of reporting. To reach compliance with the legal regulations. prescribed by generally valid legislation (autotruck drivers.12. etc. Within this system. records of occupational accidents and records of personal protective aids). gas facilities operating staff. Annual report is compiled every year as of 31. public media. unassisted.). and strives to continuously update the system. and also provides employees with personal protective aids. The company ensures regular checks on occupational health and safety as well as prescribed revisions to be performed by engineering inspector. having been performed by company itself.occupational accidents and injuries. namely through initial training in the form of educational film and assisting materials prepared by occupational safety department. spot checks are performed at the building entrance.

In addition. 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.. environment. beyond all doubt. 1996). chlorine is toxic by inhalation. The key to this definition is that the hazard is intrinsic to the material. Bollinger. 1992). An inherently safer process reduces or eliminates the hazard by reducing the quantity of hazardous material or energy. the business also chooses different communication tools. and steam at 600 psig contains significant potential energy. the basic information on corporate environmental approach and on work law relations is included in annual report. The protective layers may include one or more of the following: · The process design .holder of RC logo and based on its participation in this programme it also meets all obligations in the area of disclosure of information. or to its conditions of storage or use. This means that it is aware of the importance of communication for improving credibility of the company and its attractiveness as employer. 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. or property (adapted from CCPS. the environment. al. Such communication activity is also. a response to the requirements of the interested parties. 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. and cannot be changed. Up-to-date information is also made available to the public by means of corporate periodical. or property which is potentially impacted. To address the interested parties. or by completely eliminating the hazardous agent. These hazards are basic properties of the materials and the conditions of usage. 1993b. Annual report is placed on corporate website and is also available in the form of CD version. A hazard is defined as a physical or chemical characteristic that has the potential for causing harm to people. 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. The business regularly organizes meetings with mayors of the municipalities in the region. For example. gasoline is flammable. et. This approach is illustrated in Figure 1 (CCPS. and this reduction or elimination is a permanent and inseparable part of the process technology.

and to maintain their reliability throughout the life of the plant. and operator control · Critical alarms. the environment. an inherently safer process will allow the number of layers of protection to be reduced. 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. rather than by adding on additional safety devices and layers of protection. 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. or property. fire fighting · Community emergency response — for example. and by making each layer highly reliable (Figure 2). or by reducing the magnitude of the impact should an incident occur. both to design and build them initially. the basic process hazards remain. the layers of protection require significant expenditure of resources. However. 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. and is likely to be less expensive to build and operate because of the elimination of complex safety systems. alarms. and there is always the potential — perhaps very small. but never zero — that all layers will fail simultaneously and the hazardous incident will occur. Ideally. The inherently safer design approach is to eliminate or reduce the hazard by changing the process itself. Furthermore. . The risk can be reduced to very low levels by providing a sufficient number of layers of protection. Failure to adequately maintain the layers of protection may result in a significant increase in the process risk . The overall design is therefore more robust from a safety and environmental viewpoint.· Basic controls. operator control.

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simplify the plant. For a chemical process. However. and other physical and chemical operations to be used. rather than discovering the need for these layers of protection later on as a result of accidents and near misses. but these opportunities can result in significant improvements. the greatest potential for realizing an inherently safer process design is early in development. At this time. including the raw materials. and devices. 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. the designer still has considerable freedom in technology selection. In fact. . perhaps the greatest opportunities lie in the selection of the chemical synthesis route to be used.nship to Safety in Design Safety in Design can be based on either of the approaches described. In an existing plant. it is important to remember that it is never too late to consider inherently safer design options. there will be different kinds of opportunities for modifications to improve inherent safety. solvents. reaction steps. chemical intermediates. It may not be feasible to change the basic process chemistry and technology. but it may be possible to reduce inventory. Add-on safety features and layers of protection can be identified and incorporated during design. they should be incorporated into the process design — we should anticipate potential accidents during design and provide the appropriate protective systems. However. procedures.

and which represent a ‘once and for all’ policy decision. safety interlocks. emergency response. Strategic approaches include measures which have “wide significance.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. 1993).” Safety in Design can entail both strategic and tactical risk management approaches. Tactical approaches include measures “which are added on at a late state or those which entail frequent repetition. 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. These systems are commonly referred to as engineering controls. administrative checks. 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. There are four basic strategies for implementing inherently safer chemical processes: Minimize — Use smaller quantities of hazardous substances Continuous reactors (stirred tanks. and emergency shutdown systems to detect and correct process deviations. loop reactors. Marshall (1990) categorizes risk management strategies as strategic and tactical. Active — Using controls. or to minimize the effects of an incident. and other management approaches to prevent incidents.” Active controls and procedural approaches tend to be “tactical. Substitute — Replace a material with a less hazardous substance Water based paints and coatings Alternative chemistry using less hazardous materials . but the greatest benefits are realized from the early consideration of strategic risk management measures.” Inherent and passive approaches tend to fall into the “strategic” category. Procedural — Using operating procedures.

1986). a less hazardous form of a material. This information is used to improve procedures to prevent similar accidents in the future. or flares to contain the relief system effluent. England. and a nickel carbonyl catalyst. Simplify — Design facilities which eliminate unnecessary complexity and make operating errors less likely. including devices such as scrubbers. 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. catch tanks. . CASE STUDIES Four Significant Disasters The study of case histories provides valuable information to chemical engineers involved with safety. The newer propylene oxidation process uses significantly less hazardous materials (Hochheiser.Less flammable or toxic solvents Example: Acrylic esters were formerly manufactured using the Reppe process.6 miles by reducing the temperature of the monomethylamine from 10ºC to -6ºC . using acetylene. The four most cited accidents (Flixborough. rather than providing complex emergency relief systems.9 miles to 0. carbon monoxide. Moderate — Use less hazardous conditions. 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.

Twenty-eight people died. The process where the accident occurred consisted of six reactors in series. England The accident at Flixborough. The Flixborough accident is perhaps the most documented chemical plant disaster.9 atm). Each reactor normally contained about 20 tons of cyclohexane. Because only 20-inch pipe stock was available at the plant. 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. The British government insisted on an extensive investigation. 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. The liquid reaction mass was gravity-fed through the series of reactors.000 tons per year of caprolactam. In these reactors cyclohexane was oxidized to cyclohexanone and then to cyclohexanol using injected air in the presence of a catalyst. which has properties similar to gasoline. the cyclohexane volatilizes immediately when depressurized to atmospheric conditions. Chapter 13 presents case histories in considerably more detail. Inspection showed a vertical crack in its stainless steel structure. as shown in Figure 1-10. and 36 others were injured. Flixborough. Several months before the accident occurred. England. India. The cloud was ignited by an unknown source an estimated 45 seconds after the release. the connections to reactor 4 and reactor 6 were made using flexible bellows-type piping. The Flixborough Works of Nypro Limited was designed to produce 70. Texas) are presented here. occurred on a Saturday in June 1974. and Pasadena. As a result of the accident. Under the process conditions in use at Flixborough (155°C and 7. The decision was made to remove the reactor for repairs. an estimated 30 tons of cyclohexane volatilized and formed a large vapor cloud. Seveso. safety achieved a much higher priority in that country. The resulting explosion leveled the entire plant facility. including the administrative offices. reactor 5 in the series was found to be leaking. Upon rupture of the bypass. 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. it had a major impact on chemical engineering in the United Kingdom. a basic raw material for the production of nylon. An additional decision was made to continue operating by connecting reactor 4 directly to reactor 6 in the series. The feed pipes connecting the reactors were 28 inches in diameter. The process uses cyclohexane. Eighteen of these fatalities occurred in the main control room when the ceiling . Italy.Bhopal. Although it was not reported to any great extent in the United States.

Somehow a storage tank containing a large amount of MIC became contaminated with water or some other substance. The resulting fire in the plant burned for over 10 days.5 miles away when the plant was constructed. the scrubber and flare systemswere not . ensuring that the vapors will stay close to the ground once released. and flammable. Individuals exposed to concentrations of MIC vapors above 21 ppm experience severe irritation of the nose and throat. India The Bhopal. This accident could have been prevented by following proper safety procedures. The plant was partially owned by Union Carbide and partially owned locally. India.collapsed. MIC demonstrates a number of dangerous physical properties. The nearest civilian inhabitants were 1. Its boiling point at atmospheric conditions is 39. It is reactive. MIC is an extremely dangerous compound. Death at large concentrations of vapor is due to respiratory distress. MIC storage tanks are typically refrigerated to prevent this problem.Unfortunately. An intermediate compound in this process is methyl isocyanate (MIC). MICreacts exothermicallywithwater. a shantytown eventually grew around the immediate area.Achemical reaction heated theMIC to a temperature past its boiling point. The plant produced pesticides. The Bhopal plant is in the state of Madhya Pradesh in central India. Because the plant was the dominant source of employment in the area. with inadequate cooling the temperature will increase and the MIC will boil. and it has a vapor pressure of 348mmHgat 20°C.Although the reaction rate is slow. Damage extended to 1821 nearby houses and 167 shops and factories. Fifty-three civilianswere reported injured. This is due to the more than 2000 civilian casualties that resulted. TheMIC vapors traveled through a pressure relief system and into a scrubber and flare system installed to consume theMICin the event of a release. volatile.02 ppm (parts per million).1°C. Bhopal. on December 3. Loss of life would have been substantially greater had the accident occurred on a weekday when the administrative offices were filled with employees. The unit using the MIC was not operating because of a local labor dispute. has received considerably more attention than the Flixborough accident. 1984.Thevapor is about twice as heavy as air. toxic. The maximum exposure concentration of MIC for workers over an 8-hour period is 0. accident.

1976. civilian evacuation was not started until several days later. The reaction includes the dangerous intermediate MIC. decontamination is difficult. An alternative reaction scheme is shown at the bottom of the figure and involves a less dangerous chloroformate intermediate. On July 10. The plant was owned by the Icmesa Chemical Company. a small amount of TCDD (2. No plant equipment was damaged. The scrubber and flare system should have been fully operational to prevent the release. An estimated 2 kg of TCDD was released through a relief system in a white cloud over Seveso. The product was hexachlorophene. Inventories of dangerous chemicals. over 250 cases of chloracne were reported. killing over 2000 civilians and injuring an estimated 20. A subsequent heavy rain washed the TCDD into the soil. An estimated 25 tons of toxic MIC vapor was released. resulting in a higher than normal operating temperature and increased production of TCDD.000 inhabitants. with trichlorophenol produced as an intermediate.8tetrachlorodibenzoparadioxin) is produced in the reactor as an undesirable side-product. Seveso. with an inventory of MIC of less than 20 pounds. for a variety of reasons. Another solution is to redesign the process to reduce the inventory of hazardous MIC. Italy Seveso is a small town of approximately 17. During normal operation. TCDD is perhaps the most potent toxin known to humans. Over 600 people were evacuated. should also have been minimized.3. Animal studies have shown TCDD to be fatal in doses as small as 10_9 times the body weight.7. Because of poor communications with local authorities. The toxic cloud spread to the adjacent town. One such design produces and consumes the MIC in a highly localized area of the process. the trichlorophenol reactor went out of control. Nonlethal doses of TCDD result in chloracne. No plant workers were injured or killed. Italy. 15 miles from Milan. Approximately 10 square miles were contaminated. an acne-like disease that can persist for several years. particularly intermediates. Because TCDD is also insoluble in water. The exact cause of the contamination of the MIC is not known.000 more. If the accident was caused by a problem with the process. a well-executed safety review could have identified the problem. and an additional . By then. a bactericide.operating.

the product plugs the settling leg. and hydrogen. and the plug 13Occupational Safety and Health Administration is removed by maintenance . evidence showed that the standard operating procedures were not appropriately followed. isobutane. Second. and capital losses of over $715 million. the initiation steps would not have occurred. by following proper procedures. First. Of the 50 men assigned to clean up the release. the hazards could have been identified and corrected before the accidents occurred.2000 people were given blood tests. The release formed a large gas cloud instantaneously because the system was under high pressure and temperature. The release occurred in the polyethylene product takeoff system. encased in concrete and dumped into the ocean. India. Less than 200 g of TCDD was released. The most severely contaminated area immediately adjacent to the plant was fenced. resulted in 23 fatalities. This explosion occurred in a high-density polyethylene plant after the accidental release of 85. Texas A massive explosion in Pasadena. The Seveso and Duphar accidents could have been avoided if proper containment systems had been used to contain the reactor releases. Occasionally. by using proper hazard evaluation procedures. Pasadena. The cloud was ignited about 2 minutes after the release by an unidentified ignition source.000 pounds of a flammable mixture containing ethylene. and the contamination was confined to the plant. The damage resulting from the explosion made it impossible to reconstruct the actual accident scenario. hexane. However. the condition it remains in today. on October 23. The proper application of fundamental engineering safety principles would have prevented the two accidents. in 1963 the plant was finally disassembled brick by brick. 314 injuries.Usually the polyethylene particles (product) settle in the settling leg and are removed through the product takeoff valve. TCDD is so toxic and persistent that for a smaller but similar release of TCDD in Duphar. Texas. 1989. 4 eventually died from the exposure.

(2) the single-block (DEMCO) valve on the settling legwas not designed to fail to a safe closed position when the air failed. and (3) crowded process equipment. and the lockout device was removed. many serious safety deficiencies were ignored or overlooked. the product takeoff valvewas removed. (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. specifically. The normal—and safe—procedure includes closing the DEMCO valve.personnel. and enforcement of effective permit systems (for example. implementation. The accident investigation evidence showed that this safe procedurewas not followed. Then the product takeoff valve is removed to give access to the plugged leg. This scenario was a serious violation of well-established and well-understood procedures and created the conditions that permitted the release and subsequent explosion. Other factors that contributed to the severity of this disaster were also cited: (1) proximity of high-occupancy structures (control rooms) to hazardous operation. and as a result. . and locking the valve in the closed position. TheOSHAinvestigation13 found that (1) no process hazard analysis had been performed in the polyethylene plant. and (5) no permanent combustible gas detection and alarm system was located in the region of the reactors. the DEMCO valvewas in the open position. (4) no provision was made for the development. removing the air lines. (2) inadequate separation between buildings. line opening).

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