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.

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

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

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

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

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

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

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

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

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

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

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Relatio .

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

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

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

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

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

and an additional .operating. The toxic cloud spread to the adjacent town.000 more. over 250 cases of chloracne were reported.8tetrachlorodibenzoparadioxin) is produced in the reactor as an undesirable side-product. decontamination is difficult. the trichlorophenol reactor went out of control. The plant was owned by the Icmesa Chemical Company. particularly intermediates. The exact cause of the contamination of the MIC is not known. TCDD is perhaps the most potent toxin known to humans. The product was hexachlorophene. Another solution is to redesign the process to reduce the inventory of hazardous MIC. On July 10. civilian evacuation was not started until several days later. Because TCDD is also insoluble in water. resulting in a higher than normal operating temperature and increased production of TCDD. A subsequent heavy rain washed the TCDD into the soil. During normal operation. No plant workers were injured or killed. Approximately 10 square miles were contaminated. 1976. An estimated 2 kg of TCDD was released through a relief system in a white cloud over Seveso. Seveso. Over 600 people were evacuated. with an inventory of MIC of less than 20 pounds. The reaction includes the dangerous intermediate MIC. Animal studies have shown TCDD to be fatal in doses as small as 10_9 times the body weight. An alternative reaction scheme is shown at the bottom of the figure and involves a less dangerous chloroformate intermediate. Inventories of dangerous chemicals.000 inhabitants. Nonlethal doses of TCDD result in chloracne. By then. 15 miles from Milan. Italy. should also have been minimized. a small amount of TCDD (2. The scrubber and flare system should have been fully operational to prevent the release.3. One such design produces and consumes the MIC in a highly localized area of the process. killing over 2000 civilians and injuring an estimated 20.7. Italy Seveso is a small town of approximately 17. a well-executed safety review could have identified the problem. An estimated 25 tons of toxic MIC vapor was released. If the accident was caused by a problem with the process. for a variety of reasons. with trichlorophenol produced as an intermediate. a bactericide. Because of poor communications with local authorities. an acne-like disease that can persist for several years. No plant equipment was damaged.

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

Other factors that contributed to the severity of this disaster were also cited: (1) proximity of high-occupancy structures (control rooms) to hazardous operation. The accident investigation evidence showed that this safe procedurewas not followed. 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. and (3) crowded process equipment.personnel. (2) inadequate separation between buildings. The normal—and safe—procedure includes closing the DEMCO valve. (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. many serious safety deficiencies were ignored or overlooked. removing the air lines. specifically. and enforcement of effective permit systems (for example. the product takeoff valvewas 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. and locking the valve in the closed position. and the lockout device was removed. implementation. and as a result. line opening). the DEMCO valvewas in the open position. Then the product takeoff valve is removed to give access to the plugged leg.

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