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.

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

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

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

(3) handling larger particle size solids to minimize dust. that is.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. When possible. safer materials should be used in place of hazardous ones. using a hazardous material under less hazardous conditions. This can be accomplished by using alternative chemistry that allows the use of less hazardous materials or less severe processing conditions. toxic or flammable solvents should be replaced with less hazardous solvents (for example. 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. substitutions should also be considered as an alternative or companion concept. and (4) processing under less severe temperature or pressure conditions. Containment buildings are . Less hazardous conditions or less hazardous forms of a material include (1) diluting to a lower vapor pressure to reduce the release concentration. that is. (2) refrigerating to lower the vapor pressure. While minimization possibilities are being investigated.water-based paints and adhesives and aqueous or dry flowable formulations for agricultural chemicals). Another alternative to substitution is moderation.

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

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

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

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

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

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

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Relatio .

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

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

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. 1986). and a nickel carbonyl catalyst.Less flammable or toxic solvents Example: Acrylic esters were formerly manufactured using the Reppe process. England. Moderate — Use less hazardous conditions. 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. carbon monoxide. a less hazardous form of a material. catch tanks.9 miles to 0.6 miles by reducing the temperature of the monomethylamine from 10ºC to -6ºC . The four most cited accidents (Flixborough. or flares to contain the relief system effluent. rather than providing complex emergency relief systems. including devices such as scrubbers. using acetylene. Simplify — Design facilities which eliminate unnecessary complexity and make operating errors less likely. This information is used to improve procedures to prevent similar accidents in the future. 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. .

England The accident at Flixborough. The resulting explosion leveled the entire plant facility. it had a major impact on chemical engineering in the United Kingdom. The process where the accident occurred consisted of six reactors in series. occurred on a Saturday in June 1974. and 36 others were injured. Eighteen of these fatalities occurred in the main control room when the ceiling . Inspection showed a vertical crack in its stainless steel structure. An additional decision was made to continue operating by connecting reactor 4 directly to reactor 6 in the series.Bhopal. as shown in Figure 1-10. England. reactor 5 in the series was found to be leaking. Upon rupture of the bypass. safety achieved a much higher priority in that country. 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. which has properties similar to gasoline. Although it was not reported to any great extent in the United States. In these reactors cyclohexane was oxidized to cyclohexanone and then to cyclohexanol using injected air in the presence of a catalyst. Several months before the accident occurred. The process uses cyclohexane. the cyclohexane volatilizes immediately when depressurized to atmospheric conditions. 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 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 liquid reaction mass was gravity-fed through the series of reactors. Because only 20-inch pipe stock was available at the plant. Flixborough. a basic raw material for the production of nylon. Texas) are presented here. The feed pipes connecting the reactors were 28 inches in diameter. Italy. including the administrative offices. Under the process conditions in use at Flixborough (155°C and 7.000 tons per year of caprolactam.9 atm). an estimated 30 tons of cyclohexane volatilized and formed a large vapor cloud. and Pasadena. The Flixborough Works of Nypro Limited was designed to produce 70. the connections to reactor 4 and reactor 6 were made using flexible bellows-type piping. Twenty-eight people died. As a result of the accident. Seveso. The decision was made to remove the reactor for repairs. The Flixborough accident is perhaps the most documented chemical plant disaster. The British government insisted on an extensive investigation. Chapter 13 presents case histories in considerably more detail. Each reactor normally contained about 20 tons of cyclohexane. India. The cloud was ignited by an unknown source an estimated 45 seconds after the release.

the scrubber and flare systemswere not . The maximum exposure concentration of MIC for workers over an 8-hour period is 0. Loss of life would have been substantially greater had the accident occurred on a weekday when the administrative offices were filled with employees. Its boiling point at atmospheric conditions is 39. This is due to the more than 2000 civilian casualties that resulted. Death at large concentrations of vapor is due to respiratory distress. Bhopal. Somehow a storage tank containing a large amount of MIC became contaminated with water or some other substance. The nearest civilian inhabitants were 1.1°C. The resulting fire in the plant burned for over 10 days. Because the plant was the dominant source of employment in the area. a shantytown eventually grew around the immediate area.collapsed. MIC storage tanks are typically refrigerated to prevent this problem. has received considerably more attention than the Flixborough accident. An intermediate compound in this process is methyl isocyanate (MIC). India The Bhopal. TheMIC vapors traveled through a pressure relief system and into a scrubber and flare system installed to consume theMICin the event of a release. and flammable.Achemical reaction heated theMIC to a temperature past its boiling point. India. Damage extended to 1821 nearby houses and 167 shops and factories. accident.02 ppm (parts per million). Individuals exposed to concentrations of MIC vapors above 21 ppm experience severe irritation of the nose and throat.5 miles away when the plant was constructed. This accident could have been prevented by following proper safety procedures.Thevapor is about twice as heavy as air. The plant was partially owned by Union Carbide and partially owned locally. and it has a vapor pressure of 348mmHgat 20°C. on December 3. Fifty-three civilianswere reported injured.Unfortunately. The unit using the MIC was not operating because of a local labor dispute. MIC demonstrates a number of dangerous physical properties.Although the reaction rate is slow. The Bhopal plant is in the state of Madhya Pradesh in central India. MIC is an extremely dangerous compound. with inadequate cooling the temperature will increase and the MIC will boil. The plant produced pesticides. toxic. It is reactive. 1984. MICreacts exothermicallywithwater. ensuring that the vapors will stay close to the ground once released. volatile.

decontamination is difficult. and an additional . A subsequent heavy rain washed the TCDD into the soil. Inventories of dangerous chemicals. particularly intermediates.8tetrachlorodibenzoparadioxin) is produced in the reactor as an undesirable side-product. 15 miles from Milan. The plant was owned by the Icmesa Chemical Company. killing over 2000 civilians and injuring an estimated 20. The exact cause of the contamination of the MIC is not known. an acne-like disease that can persist for several years. over 250 cases of chloracne were reported. Approximately 10 square miles were contaminated. Seveso. The reaction includes the dangerous intermediate MIC. Italy Seveso is a small town of approximately 17.3. with trichlorophenol produced as an intermediate.7. Another solution is to redesign the process to reduce the inventory of hazardous MIC.000 more. for a variety of reasons. resulting in a higher than normal operating temperature and increased production of TCDD. An alternative reaction scheme is shown at the bottom of the figure and involves a less dangerous chloroformate intermediate. The product was hexachlorophene. civilian evacuation was not started until several days later. 1976.000 inhabitants. No plant workers were injured or killed. Italy. By then. a bactericide.operating. If the accident was caused by a problem with the process. An estimated 25 tons of toxic MIC vapor was released. The toxic cloud spread to the adjacent town. An estimated 2 kg of TCDD was released through a relief system in a white cloud over Seveso. Nonlethal doses of TCDD result in chloracne. a well-executed safety review could have identified the problem. Because TCDD is also insoluble in water. should also have been minimized. During normal operation. TCDD is perhaps the most potent toxin known to humans. with an inventory of MIC of less than 20 pounds. a small amount of TCDD (2. Over 600 people were evacuated. No plant equipment was damaged. One such design produces and consumes the MIC in a highly localized area of the process. the trichlorophenol reactor went out of control. On July 10. The scrubber and flare system should have been fully operational to prevent the release. Because of poor communications with local authorities. Animal studies have shown TCDD to be fatal in doses as small as 10_9 times the body weight.

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

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

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