CHAPTER 26 Health, Safety, and the Environment WHAT YOU WILL LEARN * The basics of heatth, environment, and safety One goal of chemical engineering is to produce goods and services that enhance the quality. of ife. Chemical engineers have been at the forefront of efforts to improve health (e.., phar- ‘maceuticals), safety (eg, shatterproof polymer glasses), and the environment (eg, catalytic converters). Moreover, throughout the product life cycle, chemical engineers are concerned with potential harm to the health and safety of people and damage to the environment. This chapter focuses on assessment of these potential dangers. Chapter 27 focuses on proactive strategies to avoid them. Although many of the chemical processing industries regard improvements of health, safety, and the environment (HSE) as one general function, the US. government has separated the field into distinct categories, based on the varying rights afforded to dif- ferent classes and for historical purposes. The health and safety of employees, for example, is zogulated by the Occupational Safety and Health Administration (OSHA), whereas the health of nonemployees and the environment are regulated by the Environmental Protet- tion Agency (EPA). Other activities are regulated by the Department of Transportation (DOT) or the Department of Energy (DOB), among other agencies. 4 An exact description of applicable laws, rules, and regulations would be out of date before any textbook could be printed; rather, this chapter describes the types of regulations that are relevant to chemical engineering and provides guidance on where to find the current (and proposed) regulations. The focus is on the general concepts and strategies of 3 risk assessment and reduction that transcend the details of regulations.2886 26.4 Section V- The Impact of Chemical Engineering Design on Society RISK ASSESSMENT 26.1.1 Accident Statistics Engineers quantify risks to provide a rational basis for deciding what activities should be Undertaken and which risks are worth the benefits provided. These dense are fre Hontly made by nonengineers; thus, itis essential that the measures thee engineers use he ria, Tae Hay oF workelated ines that resus ina "ost workday” oocoten the ratio. Thus, minor injures that can be treated with fist aid see oy counted, but to improve the safety of chemical plants, auiniter observation is that there are differences in relative rankings if one uses the Sifferent risk measurements, Perhaps most striking is that the FAR ne employees Fpeenical industry is only slghlly higher than the FAR for people staying in their homes. However, this isa potentially misleading comparison. ‘The portion of te ‘population that i | {Chapter 26 Health, Safety, andthe Environment 887 Table 26.1 Comparison of Three Risk Measurements [1] OSHA Incident Rate Fatal Accdent Rate Fatality Rate (Injures and Deaths “(Deaths per (Deaths per Person Aetivity er 200,000) 100,000,000 h) per Year) Working in chemical industry 049 4 Staying at home Working in stel industry 154 8 Working in construction 388 @ Traveling by car a 70x 108 Rock climbing 4000 40x96 Smoking (1 pack per day) 5000 10 Being struck by lightning o1x age ‘works is on average more healthy than the portion that does not. Also, most people take risks at home that they would not be allowed to take at work. Finally, a worker is probably ‘more tired and prone to accidents at home after a hard day at w ‘The main use of these statistics is not to compare one activity with another (unless they can be substituted for one another) but to monitor improvements to the health and safety of workers and others achieved by process modifications. 26.1.2 Worst-Case Scenarios Another measure of risk is to imagine the worst possible consequence of an operation. Such a study is called a worst-case-scenatio study, and it is required by some govemment agen- cies. These studies have some drawbacks, but they can be very useful in identifying ways to avoid serious accidents, A related strategy that is routinely used throughout the industry for identifying potential hazards is celled HAZOP and is discussed in Section 26.4. ‘The development of worst-case scenarios is certainly subjective, but government agencies and organizations develop guidelines for this task. For example, there is cer- tainly a chance that an asteroid will impact Earth directly in the middie of the chemical plant. Should this be the worst-case scenario? Most people would argue that this takes the ‘worst-case scenario study beyond reason, but there are no clear-cut rules. The subjective rules that Rave been developed contain definitions such as the worst accident that might reasonably be assumed possible over the life of the facility. Different people would define “possible” (or “probable”) in different ways. Is sabotage by an employee possible? Is the simultaneous failure of three independent safety systems probable? Certainly the events ‘of September 11, 2001, have indicated that a terrorist-attack scenario is not impossible. Sometimes probabilities of occurrence can be estimated, but often they cannot, By EPA definition (0CFR68.3), “Worst-case release means the release of the largest quantity of a regulated substance from a vessel or process line failure that results in the greatest distance to an endpoint defined in § 68.22(a).” This end point is a specified con- centration of a toxic substance, an overpressure of 1 psi for explosions, a radiant heat flux of 5 kW/m? for 40 seconds for a fire, or the lower flammability limit for a flammnable sub- stance, whichever is appropriate. ‘Thus, the worst case is defined by the size of the area adversely affected by the release. There are also definitions of how much of the material26.2 in a tank (often 100%) shou in the scenatio, management tantly cs analyses are required by wegen smnese guidelines are constantly changing, so they are not described in detail hevy ‘The most current guidelines should be obtenel okt the EPA, OSHA, or other agencioe 26.1.3 The Role of the Chemical Engineer As the professional-with the best kno chemical processing operation, the ty that it could understand. When soamag atively minor accidents occur, many feel the seemed to have said that there were no REGULATIONS AND AGENCIES whe pedo Pending regulations are also giver in the Fe, Rally, the regulations ofa space type ane een ‘and published in the Code of Federal Regulations (CER), Both the FR and the erie lable in lange libraries and in all av {Sbtares, as wells on the internet In Table 2oe the Internet addresses for the FR and CER ao the date thio book is writen are proviiea Because Intemet addresses change fre: EngRUY the use ofa search engine to find new Uione Suggested if the links given here are broken, However, note that only server address ending in “gov” are official US, govern. ment Web sites. ‘erous private firms collate federal ), and they sell their compendia,Sooke ys ake ease Chapter 26 Health, Safety, and the Environment. 389 Table 26.2 Internet Addresses for Federal Agencies Code of Federal Regulations (CFR) —_http://www.gpa.gow/fésys Federal Register (FR) and US.Code _hitp://vrww.gpo.gov/fdsys DOT regulations (FRand 49 CFR) ~ _http://worw-phmsadot gov /hazmat/regs EPA regulations (FR and 40 CFR) itp: / /wwww.epa.gov /lawsregs MSHA regulations (FR and 90 CER)’ —_hitp://www.msha gow /regsinfo.htm NIOSH databases hitp://www.cde gov /niosh /database html OSHA regulations (Rand 29 CFR) —_hitpe//warwoaha.gov State and local government regulations are also available in hard copy and increas- ingly in online form, However, itis best to contact these agencies directly to be sure that one hhas all the relevant regulations. Nongovernmental organizations ean be contacted directly for their rules. However, sources of information on the Internet are rotoriously inaccurate and out of date, Unless itis an official government Web site (with the date of the latest update), beware. 26.2.1 OSHA and NIOSH In general, the Occupational Safety and Health Administration promulgates regulations having to do with worker safety and health in industries other than mining (Mine Safety and Health Administration, MSHA, serves a similar role there). The National Institute for Occupational Safety and Health (NIOSH) is a federal research organization that provides information to employees, employers, and OSHA to help assess health and safety risks. Regulations are not promulgated by NIOSH, although it does certify various analytical techniques and equipment (such as respirators). ‘One major law and five major regulations in this area are the OSHA Act [2], Hazard Communication (29CFRI910.1200), Air Contaminants (29CFR1910.1000), Occupational Exposure to Hazardous Chemicals in Laboratories (@9CFR1910.1450), Hazardous Waste Operations and Emergency Response (26CFR1901.120), and Process Safety Management of Highly Hazardous Chemicals (29C#R1910.119). OSIIA Act and Air Contaminants Standard. The original act of Congress that set up OSHA, the Occupational Safety and Health Act of 1970 [2], specified certain regulations and standards and required OSHA to promulgate others. Pethaps of most importance is the so-called general duty clause of the OSHA’ Act stating that “each employer shall fur- nish (o each of his employees employment and a place of employment which are free from recognized hazards that are causing or are likely to cause death or serious physical harm to his employees” (Reference 2, Section 5.2.1), This clause has been interpreted to mean that an employer must avoid exposing employees to hazards that should have been known to the employer, whether or not that hazard is specifically regulated by OSHA. Thus, the respon sibility of researching the literature to see whether anyone has identified a hazard is placed fn the employer. Most chemical engineers are employees, and yet they often represent the ‘employer and therefore assume the responsibilities under the general duty clause. To search for published data on chemical hazards, a good place to start is the Inte- grated Risk Information System (IRIS), the Hazardous Substances Data Banik (HSDB), and other databases at http:/ /www-oxnet.nlm.nih gov.Section V_ The Impact of Chemical Engineering Design on Society these exposure limits i based on the assumption that atypical that concentration of the substance for eight hours a day, five d over the shift is not greater than the PEL. When even short teem, exposure to higher levels fi harmful, there is a separate short-term exposure limit (STEL), which is a'Isevinens time-weighted average concentration that must never be exceeded, or an OSHA ceiling Soucentration whichis an instantaneous concentration that must never be exceeded, Als craps concentrations from which one could escape within 30 minutes Without expan, soars escape-impaiting ot irreversible health effects are identified as immediately ian, ree lands the hazards; dhs, mich effort in taining goes into satisfying this requirement ‘hwo very sbvious results and requirements of this regulation are proper labeling of con- Rivers And availabilty of material safety data sheets (MSDS), Table 263 lists typicel es eactons of an MSDS, but the precise format of an MSDS isnot presently defined by {eBulation, although some of the minimum requirements are, and these are sso listed 7, ‘ble 263. The MSDS must list the substances, their know hazards, and procecuves for i F é : : i i £ ? 3 & B J g e : 8 Unfortunately, often MSDS are difficult to read quickly. They are filled with mech useful information,Chapter 26 Health, Safety, and the Environment 291 Table 26.3 Typical Sections of a Material Safety Data Sheet (SDS) 1. Material and manufacturer identification, 2, Hazardous ingredients /identity information 3, Physical/Chemical characteristics 4, Fire and explosion hazard data 8, Reactivity data 6. Health hazard data 7. Precautions for safe handling and use 8. Control measures From OSHA Form 1218-0972 ‘They must be studied extensively bore any hazardous situation is encountered. A group of intemational agencies (UN Environment Programme, International Labour Office, and the World Health Organization in cooperation with NIOSH and the European Community) has developed a simpler, standard, two-page data card that can be understood quickly and used in an emergency. In addition to the required MSDSs, the ready availability of this, intemational chemical safety card wherever a hazardous material is used, stored, or trans- ported is highly recommended, They can be found at hitp://www.edegov/niosh/ ipes/ jpescard html. a June 1, 2007, the European Community put into force a new regulation called Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), Although it specifically applies to manufacturers within the European Union and manufac ‘turers that import into the EU, it is becoming the de facto worldwide standard for regula a tion of chemical products, All firms that handle one metric tonne ot more per year of any F chemical product or produce any chemical product that is new to commerce are covered, For many existing chemical products, new data have been measured to determine hazards : more accurately, Substances that are high-volume, mutagenic, or very toxic to aquatic or- ganisms have already been fully phased in. Other low-volume substances will be phased in through May 2018, Details ofthe regulation are available at hitp://echa.europa.eu, ‘Minimum Requirements for MSDS (29CFR1910.1200{g)). An MSDS is required for each “hazardous chemical,” including those specifically listed in 29CFRI910 (subpart Z), any material assigned a TLV, or any material determined to be cancer causing, corrosive, toxic, an irritant, a sensitizer, or one that has damaging effects on specific body organs, ‘There are numerous facts that may be given in an MSDS; however, the minimum infor- sation required is listed below. 1. Written in English. 2. Identity used on label. 3. Chemical name and common name of all ingredients that are hazardous and that are present in 21% concentration or that could be released in harmful concentrations. 4. Chemical name and coinmon name ofall ingredients that are carcinogens and that are present in 2 0.1% concentration or that could be released in harmful concentrations. 5. Physical and chemical characteristics of the hazardous chemical (such as vapor pressure, flash point).892 Section V_The Impact of Chemical Engineering & Physical hazards ofthe hazardous chemical, including the potential for and reactivity. ial including signs and symptoms of expo. sure, and any medical condi i by exposure to the chemical 8. Primary routes of entry. 9 OSHA permissible exposure limit, ACGIETTLY, ancl any other exposure limit used precommended by the chemical manufacturer, importes or employer. : 10. Whether the hazarclous chemical is listed inthe National Toxic : Catan ean the International Agency for Research on Cancer (ARC) Monographs (atest editions), or by OSHA, | 11. Any generally applicable precautions for safe hand the chemical manufacturer, importer, or employer preparing the MSDS, including OF condones glen practices, protective measures during Tepair and maintenance of contaminated equipment, and procedures for cleanup of spills and leaks ; 12 Aay generally applicable control measures that are knows fhe chemical manufac. {cree importer, or employer preparing the MSDS, suche appropriate engineering puntols, Work practices, or personal protective equipment 15, Emergency and first aid procedures, Ta, Rate of preparation of the MSDS or the lst change to it 15, Name, address, and telephone number of Ployer, or other responsible party preparing or distributing the material safety data Sheet that ean provide additional information on dee ‘hazardous “pPropriate emergency procedures, if necessary. ing and use that are known to Table 26.4 Process Safety Management of Highly Hazardous Chemicals (29CFR1910.129) 1, Employee participation 2. Process safety information 9. Process hazards analysis 4. Operating procedures 5. Training 6. Contractors 7. Pre-stactoup safety review 8. Mechanical integrity i 9. Hot work permit 10, Management of change 11, Incident investigation 12, Emergency planning and response 13. Compliance safety auditChapter 26 Health, Safety, and the Environment 893 that transportation of hazardous materia is roguted by the US Department of Trans- portation under 49CFR100 through 49CFRI8S ent kinds of hazards, When OSHA promulgated the Prot ir tines pit; dlteady existing rules of the American Institute of Chom iat Engineers 3 lines for Technical Management of Chemical Process Institute's Recommended Practices 750 (6] as essentially gave the force of law t6 these volun * Guide. Safely {5] and the American Petroleum les. In fact, as is often the case, OSHA ary nongovernmental standards, fracess safety management (PSM) embraces neatly the entine safety enterprise of a chemical process organization. It requires employee train ing, written operating proce- dures, specific quality in the engincering design of component ont systems, very specific 1 imployee Participation: The employer must actively involve the employees in the development and implementation ofthe safety programm, Employees are more likely are eeiand the hazacds and to follow the established safety procedanee are they ike involved early and continuously in the development of fae safety program. This item was added to the earlier APL and AIChE standard 5 (iocess Hazards Analysis: Before a process is started up and periodically thereafter (opically every thre to fve years or whenever significent modifi are made), Ssecallad study must be made ofthe process to determine potential hess and fo Correct them, There are several approved procedtur Process upset, 5: Training: The employer must train all employees in the har Procedures for mitigating them. 6 Contractors: The em; ards present and the894 Sacton V_ The Impact of Chemical Engineering Design on Society must be documented al any deviation ofthe plantas built from the des tatters mutbe acces eae 8, Mechanical Integrity: Vesels and other equipment must meet existing codes and be inspected during manufacture and efter installation, Appropriate procedures ne maintenance must be developed and followed. 9. Hot Work Permit: This sa very specific proce by which a wide range of people in the plant are notified before hot work, such as welding, can occur. Many eheeee cal plants use flammable materials, and everyone in the area needs to be informed so that no flammable vapors are released during the operation 10, Management of Change: During accident investigations in the chemical proces dstries, thas often boen found that severe incidents (involving deaths and massive destruction) occurred because equipment, procesces, or procedres were changed from the original design without careful study ofthe consequences. Thus, the OSHA regulation requires companies to have in place a system by Which any modifation reviewed by all ofthe appropriate people For example, any change in the reactor de sign must be reviewed not only by the design engineer but alo by the process engh reer who can evaluate how the overall proces is affected. The maintenance leager must also make sure thatthe modification does not adversely affect the maintenance schedule othe ability of workers to get to orto maintin the equipment. 14, Incident Investigation: When there isa hazardous process upset, it must be investi gated and a written zeport must be developed indicating the detals ofthe incident, the probeble cause, and the steps taken to avoid future incidents 12, Emergency Planning and Response: There must be a written plan, and employees rust be trained to respond to possible emergency situations Compliance Safety Audit: Periodically all of te elements of the safety system (in cluding items 1-12 above) must be edited to make sure that the approved proce- dures are being followed and that they are effective 13. One item that is included in the industry codes but not in the PSM regulation is the entry of workers into confined spaces. This situation—in which the environment of the space or the difficulty of egress from the space could create a hazard—is encountered fre- quently in the chemical process industries. OSHA regulation 29CER1910.146 covers the required permitting procedures to ensure that workers are protected in confined spaces. 26.2.2 Environmental Protection Agency (EPA) ‘The role of the EPA is to protect the environment from the effects of human activity, Although this is a very broad role, in the context of the chemical processing industries it usually relates to emissions of harmful or potentially harmful materials from the plant site to the outside by air or by water. There are three classes of such emissions: (1) planned emissions, (2) fugitive emissions, and (3) emergency emissions. This section describes some of the present regulations for these classes of emissions, There are many more regulations that are not mentioned here. In any facility, one must keep constantly aware of new and modified regulations through research, use of an environmental compliance consulting firm, or communication with the local, sate, and federal environmental protection agencies Planned Bmissions, Any process plant will have emissions, These may be harmful to the environment, benign, or, in rare cases, beneficial. In any case, a permitis uswally re- quired before construction or operation of the plant. Significant modifications to the plant‘Chapter 26 Health, Safety, and the Environment 895 (especially if they change the design emissions) will likely require a modification to the permit or anew permit. ‘These emissions permits are normally obtained through the state environmental protection agency, but federal regulations must be met, In some regions, states, or local fies, the requirements for the permit may be significantly more stringent than the federal EPA regulations. One must contact the local agencies, However, searching the EPA data- ‘bases described in Section 26.2 can provide a good preliminary overview. Permits frequently require an extensive environmental impact statement (EIS) de- tailing the present environment and any potential disturbances that the planned activity could produce. For process plants, these ElSs are typically written by a team of chemical engineers, biologists, and others, and they deal not only with planned emissions but also with potential process upsets and emergencies. In this regard, the worst-case scenario ‘mentioned in Section 26.1.2 is used. Permitting is based on assessment of potential degradation of the environment, and thus both the level of emissions from the plant and the present level of contamination in ‘the local environment are considered. There are National Ambient Air Quality Standards (NAAQS) for a few materials and National Emissions Standards for Hazardous Air Pollu- fants (NESHAP) and New Source Performance Standards (NSPS) for these and others Major sources (defined as those plants that emit more than some annual threshold quan tity such as 25 tons of hazardous air pollutants) must meet the most stringent emissions criteria and require move permits, Similar standards are applied for water quality and for discharges into the water, Many of these regulations are based on the Clean Air Act and, Clean Water Act, among others. Beyond the effects on the environment after emissions are fully dispersed in the air or the water, there can be acute, short-term effects on nearby populations. Often chemical engineers perform dispersion studies to determine the range and longevity of the plume of harmful materials that flows from the point of discharge into the air or water, ‘The focus of the Clean Air Act Amendments of 1990, Title I, is the release of volatile organic compounds (VOCS), which ace precursors to the photochemical production of ozone (smog), especially in areas that have not attained NAAQS. The definition of a VOC is any organic compound with an appreciable vapor pressure at 25°C that participates in ‘atmospheric photochemical reactions. It does not include methane, ethane, and a number of other substances listed in 40CFRS1.100(6). Hazardous air pollutants (HAP) are also regulated through Title IT of the act. An important part of planned emissions are so-called fugitive emissions. These are losses from seals in cotating equipment (eg, pumps, agitators, compressors), losses through connections between equipment (eg., piping connections, valves), and other losses ‘that result from incomplete isolation of the interior ofthe process from the atmosphere (e.g., tanks). Although substantial progress has been made over the last two decades to reduce fugitive emissions through improved equipment design, fugitive emissions are still sub- stantial and are, in some eases, the major source of all emissions from a process plant. Emergency Releases, Process upsets can create catastrophic releases of hazardous materials, and regulations require that there be an effective plan to deal with these occur- ences and that the consequences for affected populations not be too serious. As mentioned earlier, worst-case scenarios and dispersion modeling are used to make this assessment. One such regulation is the Emergency Planning and Community Right to Know Act (EPCRA) of 1986, also known as SARA, Title TI. This regulation requires plants to pro- vide the local community with information about potentially hazardous or toxic materials896 Section V_The Impact of chemical Engineering Dest on Society Sent A local emergency planning committe is formed of mer bores the local govern, facades Baney Tesponse organizations, and plant personnel, Aleo releases of certain hazardous substances must be reported to the EPA cede compilation of these releases Fhrough the DOT, regulations require all over-the-road transport vehicles to cary 4 Puapitest of hazardous materials that is immediately available tc ah emergency personnel Hone evant of an accident, Also, the DOT and the U.S, Coot Gouna regulate the condi. fans under which hazardous cargo can be transported. For example, these regulations ‘frequently require stabilizing additives to prevent runaway polymerization, The National Response Center (1-800-424-8802) is opersted by the US. Coast Guard {to serve as the sole national point of contact for reporting al oil, chemical, radiological, Response Team as well as to vasious goverment agencies that hear, incident databases, itany other EPA regulations that are beyond the scope ofthis Fock impact the opera- fot RR aaal processing facilites, including the Resource Consent and Reco AG IRCRA): the Comprehensive Environmental Response Compensation, and Liability (Ganga 2: Supestund (CERCLA); the Supertind Amenlinent sen ‘Reauthorization Act (SARA); and the Toxic Substances Control Act (TSCA). vice de ocr ant releases, and to minimize the consequences pf meen releases HPA to occur” [Reference 7, Section 1121). The RMEL aver Ie registered with the EPA, they must be made public, and they must be Periodically updated. The risk man- dive elec ey Which includes as a subset the risk manageant, plan, must include three elements: * Hazard assessment * Prevention + Emergency response This'program is coordinated with OSHA’s process safety management (PSM). In fact, compliance with the PSM of the RMP. The following ov. plants covered under the P: Process industries, Standard is considered equivalent to the prevention part frview of the risk management program pertains to all ‘SM standard, which includes most plants in the chernicaly FE Ghapter 26 Heatth, Safety, andthe Environment 897 a C ‘The hazard assessment must include a worst-case analysis, an analysis of none 2 | ‘worst-case accidental releases, and a five-year accident history. The worst-case release a scenario is defined by the EPA [40 CFR 68] as 3 the release of he largest quantity ofa regulated substance fram a vessel or process line failure, in- 7: cluding administrative controls and passive mitigation that limit the total quantity inoolved or the é release rate. For most gases, the worst-case release scenario assumes tha the quantity is released i i \ - 10 minutes. For liquids, the sconario assumes an instantaneous spi: the release rate to the ar ie os the volatilization rate fom a poo! 1 cm decp unless passive mitigation systems contain the sub. ae stance in a smuller arc. For flaraables, the worst case assumes an instantaneous release and a a ‘mnpor cloud explosion ee ‘The EPA rule specifies default values of wind speed, atmospheric stability class, and i other paraineters for the development of the offsite consequence analysis of worst case : a scenarios. Italso specifies the end point forthe consequence analysis, based on the calcu. i lated concentration of toxic materials, the overpressuce (I psi) from vapor cloud explo- : oe sions, and the radiant heat exposure for flammable releases (5 KW /me for 40 seconds). ie ‘The prevention programm is identical to the PSM standacd, except that the emergency ee: planning and response item is covered uncer a separate category in the RMP. ' i : ‘The emergency response program portion ofthe risk management plan is coordinated ; 3 with other federal zegulations, For example, compliance with the OSITA Hizasdous Waste * and Emergency Operations (HAZWOPER) rule (29 CFR 1910-120, the emergency planning tt ; 4 and response portion of the PSM standard, and EPCRA wll satisfy this requirement in the | ioe RMP regulation k § +: ‘The RMP must designate a qualified person or position with overall responsibility t : for the program, as well as show the lines of authority or responsibility for implements. : tion of the plan | é j Overall then, the only additional RMP requizement for plants already covered by f é a the OSHA process safety management regulation is the hazard essessment (cluding off é site consequence analyses of worst-case and non-worst-case accidental release acenatios) é This hazard assessment must not be confused with the process hazard analysis (PHA). ; ‘The hazard assessment isa study of what will happen in the event of an accidental release ' a | and usually ineluces, for example, air dispersion simulations. The PHA (eg, HAZOP) { ¢ | studies the hazards present in the process and seeks to minimize them through redesign i : cr modifications to operating procedures. l es 26.2.3 Nongovernmental Organizations \ ® i Many professional societies and industry associations develop voluntary standards, and : these are often accepted by government agencies and thereby are given the force of law. : ‘Examples of such organizations and their standards are as follows: IT ‘+ American Petroleum Institute (API), Recommended Practices 750 * American Institute of Chemical Engineers (AICHE) i Center for Chemical Process Safety (CPS) ! Design Institute for Emergency Relief Systems (DIERS) : + American National Standards Institute (ANSI ! fe + American Society for Testing and Materials (ASTM) a é + National Fire Protection Association (NFPA), fie diamond . ‘+ American Conference of Governmental Industrial Hygienists (ACGIH), TLVs i26.3 Section V" The Thpact of Chemical Engineéring Design on Soci + American Chemistry Counci, Responsible Care program 5 Sythetie Organi Chemicals Manufacturers Association (SOCMA) * American Society of Mechanical Engineers (ASME), ety Doiler and pressure vessel code The Responsible Care program is a chemical industry initiative started Ene members ofthe American Chemistry Couneil (about 160 companica) well as sey creroutes industry organizations inthe United States and in 50 other eeuntsne agree to Fee acotding t6 this health, safey, and environment code. The details ave siven on the ACC Web site (atp://ww americanchemistry.com). Its key areas necks in 1988, ay 1. Environmental impact | 2. Employee, product, and process safety 3. Energy 4. Chemical industry security & Troduct stewardship: managing product safety and public communications 6. A ccountability through management system certification 7. Contribution to the economy FIRES AND EXPLOSIONS ‘The most common hazards on many chemical plant sites are fires and explosions. When- Sra, feel, an oxidizer, ancl an ignition source are present, such a hazard ena Detailed gralyses ofthese hazards and their consequences are covered in other bowie’ (1,8), Here, the terminology of the field is introduced. 26.3.1 Terminology (0 its normal rate for room temperature. sonrevat if a certain temperature (the auto-ignition temperature) exceeded, the ee petted by the oxidation is euficient to sustain the tempemture evenirne extemal heating source is removed. Thus, above the auto-ignition temperature Will expand into other areas having appropriate ‘mum energy required to heat a small zepion to i ‘ignition energy and is often exceedingly small A gaseous mixture of fuel and air willChapter 26 Health, Safety, and the Environment 899 The flash point of a liquid the temperature at which the vapor in equilibrium with the standard atmosphere above a pool of the liquid is at the LFL. Thus, a low flash point indicates a potential flammability problem if the liquid is spilled. Diesel fuel, for example, is much safer than is gasoline because diesel has a higher flash point. Regulations for trans- portation and use of gasoline are therefore much more stringent than they are for diese Flash point can be measured by the open-cup or the closed-cup method. In the open-cup method, an open container of the liquid is heated while a flare-up of the vapor is intention- ally attempted with an ignition source. The temperature at which flare-up occurs is the flash point, In the closed-cup method, the liquid is placed in a closed container and allowed to come to equilibrium with air at standard pressure. Ignition is attempted at in- creasing temperatures, Although the open-cup and closed-cup flash points for many mate- tials are very close, materials that vaporize slowly and disperse in the atmosphere quickly can have much higher open-cup flash points than their closed-cup flash points. Although the MSDS will give the flash point, one must notice which type of flash point is being reported. Explosions are very rapid combustions in which the pressure waves formed propa- gate the combustion. The combustion creates a Ioeal pressure increase, which heats the fiammable mixture to its auto-ignition temperature. This secondary combustion causes the pressure wave to propagate through the mixture. This traveling pressure pulse is called a shock wave. Often, a strong wind accompanies the shock wave, The combination of shock wave and wind, called a blast wave, catises much of the damage ftom explo- sions. When the shock wave speed is less than the speed of sound in the ambient atmos- phere, the explosion is called a deflagration. When the speed is greater than the speed of sound, the explosion is called a detonation. Detonations can cause considerably more damage from the combination of blast wave, overpressure, and concussion. ‘The damage from an overpressure of only 1 psi on structures can be extensive. Such a pressure differ- ential on a typical door, for example, would result in considerably more than one ton of pressure on the door—enough to break most locks. OF special concen when flammable gaseous mixtures (or dispersions of com- bustible dusts in air) are present is the so-called vapor cloud explosion (VCE). If there is a natural gas leak, for example, the cloud (mostly methane) will spread and mix with air. ‘The cloud, parts of which are within the flammable limits, can be quite large. If it ignites, the deflagration will cause a shock wave perpendicular to the ground that can cause great damage, often flattening buildings. When a liquid stored above its ambient boiling point suddenly comes in contact with the atmosphere (through a rupture in the tank, for exam- ple), the rapid release and expansion of the vapor can cause a massive shock wave. This phenomenon is called a boiling-liquid expanding-vapor explosion (BLEVE). The failure of a steam drum, for example, can cause a BLEVE. When the BLEVE is of a flammable substance, the resulting cloud can explode. This combination of BLEVE and VCE is one of the most destructive forces in chemical plant accidents, ‘The classic example is a propane tank that ruptures when it becomes overheated in a normal fire (a BLEVE). The propane is stored as a liquid under pressure. As the tremendous quantity of propane that vapor- izes mixes rapidly with the atmosphere, it creates a massive VCE. Runaway reactions are confined, exothermic reactions that go from their normal ‘operating temperatures to greater than the ignition temperature; that is, they liberate more heat than can be dissipated. Thus, the temperature increases, increasing the reaction rate, Although there may be a steady state at a higher temperature (as there is in combustion), often the limits of mechanical integrity of the reaction vessel are reached before that point,26.4 Section V_The Impact of Chemical Engineering Design on Society Tasane catastrophic failure ofthe vessel. Such a failure can cause direct injures, release toxic material, cause a fire, or lead to @ BLEVE and/or a VCE. 10% increase in ‘increased heat transfer area is the cost of an A common scenario for an accident involving an exothermic reaction is thé loss of Seolant accident (LOCA). Unless the cooling system is backed up to the extent that ite essentially 100% reliable, one must consider this scenario in designing the vessels andl the ressure-tlief systems. 26.3.2 Pressure-Relief Systems Pung a severe process upset, the pressure and/or temperature limits of integrity for ves: gels can be approached. To avoid an uncontrolled, catastrophic release of the contents oy the destruction of the vessel, pressuxe-relief systems are installed, Usually, these are wee Yalves on vessels ot process lines that open automatically at a certain pressure, Downe, Strsam, they are connected to lares (or laminable or toxic materials), serubbers {for revle ierials) ora stack directed away from workers (for materials such as steam that present physical hazards). The design ofthe pressure-relief system is especially important Reese {he worst-case scenario must be considered, which is sometimes the simultancovs fallnns ‘of multiple relief systems, as was the case for the Bhopal tragedy in 1984, The design of such systems is complicated by several factors, The devices are de- ‘Sires {© operate under unsteady conditions, Therefore, a dynamic simulation is roqused, Also, the flow through the relief system may be single-phase or two-phase flow. Det twa, phase flow, not oly are the calculations more difficult, but also more factors affect the pres ‘sure drop, such as whether the line is horizontal or vertical Jn addition to the relief valves (which are called safety valves, relief valves, Pressure-relief valves, or pop valves depending on service), rupture disks are wced ty GPa the process to the discharge system, Rupture disks are specially manufactured lsks that are installed in a line, similar tothe metal blanks used between Flanges to close a fine permanently. However, the disks are designed to fil rapidly at a set pressure Ide. ally, the rupture disk allows no flow when the pressure is ess than the set pressure, and it Tuptures immediately, offering no resistance to flow, when the presoure hits the set point PROCESS HAZARD ANALYSIS. Pinder the “Process Hazard Analysis” requirement of the Process Safety Management of Ehghly Hazardous Chemicals regulation (29 CFR 1910-119), employers must complete ‘such an analysis ofall covered processes using one or more of te following techniques: + What * Checklist + What-lf/checklist Reel metaChapter 26 Health, Safety, and the Environment 901 I + Failure mde and effects analysis (FMEA) | Hi + Fault-tree analysis (FTA) ‘+ Hazards and operability study (HAZOP) ! or “an appropriate equivalent methodology.” The OSHA regulation specifically refers | to the AICHE Center for Chemical Process Safety for details of process hazard analysis methods [9], which is an excellent source for details of these techniques. | The whatif technique involves a group of engineers and others going through the ; fowsheet and operating procedures methodically and considering what would happen if ! i something were not as expected. For example, What ifthe reactor were not at the speci- i fed temperature? The answers to these hypothetical situations can uncover potential hay problems, This process hazard analysis technique is normally used only for simple, small 4 seale processes, such as laboratory experiments. For more complicated processes, the more rigorous HAZOP technique is used. This technique, which is described in the next i section, is a formalized version of what-if ‘ Cheekdists have been developed by various companies for their specific processes. ‘These lists can include hundreds of items (1, 9]. Checidists are very specific and focused; they a do not typically lead to the identification of safety problems that have never been encoure ol tered. Therefore, checklists (which are focused on areas of known concer) are often used in Ec combination with what if techniques (which are focused on thinking “outside the box”). A ‘The FMEA was invented by NASA in the 1960s, The underlying principle is that failures of individual components cannot be avoided, but these component failures must | ot cause a catastrophic failure of the system, Therefore, the analysis begins by identify. \ ing the various ways that each individual component can fail (a failure mode). Then the i cffect of these failures (individually and in combination) is studied. FMEA is thus a bot. i tom-up approach that leads to identification of critical combinations of component fail- : ures that can cause some catastrophic failure, The result is usually an attempt to improve the reliability of specific components ar to design protective redundancy into the system. In principle, FMEA requires the prediction and consideration of all failuze modes of all ; ‘components—a very large task for a complex system. ft FTA is based on the premise that many of the component failure modes that would \ be studied in the FMEA technique would not contribute to any system failure. FTA is a top-down analysis of the system failures. First, the catastrophic system failures to be ji avoided are identified. Then contributing failures of subsystems and individual compo. i nents are considered. FTA is widely used in the nuclear power industry, where catas strophie system failures are clearly defined. In both the FTA and FMEA analyses, large logic diagrams are created to show the connections between low-level failures and higher-level failures, Ifa combination of fail lures is required to create a higher-level failure, the connection is denoted as an AND gate Hf any one of several failures can create a high-level failure, the connction is denoted as an OR gate, There can be many levels of failures, dozens of systems failures, and several { failure modes for each of thousands of components. This logie diagratn leads directly to ' ‘the probability of system failure if the reliability of the individual components is known 4 26.4.1 HAZOP uy ‘The most widely used process hazards analysis technique in the chemical process indus- en ties is HAZOP. Unlike FTA and FMEA, the HAZOP technique is an outside-the-box feta t technique. It is a modified brainstorming technique for identifying and resalving process iSection V_ The Impact of Chemical Engineering Design on Society hazards by considering seemingly unusual occurrences. Although it is a bottom-up tech nique, it is more efficient than the FMEA because it involves early dismissal of compo. nent failure modes that are of no consequence to system operation and focuses early on the more probable failure scenarios. A HAZOP is especially useful in identifying human, factors that can contribute to system failures. For example, a HAZOP based on a sabotage scenario could consider failure modes not apt to be uncovered by the FMEA. HAZOP consists of asking questions about possible deviations that could occur in the process (or part of a process) under consideration. A HAZOP is always done in a group, and the regulation requires that the team have “expertise in engineering and process operations,” have “experience and knowledge specific to the process being evaluated,” and be “knowledgeable” about the HAZOP methodology. As with any brainstorming process, the ideas and suggestions can come very quickly, and there must be an identified seribe ready with appropriate software to capture them. Various software packages are available to speed this process and to offer additional triggers in the brainstorming process. The first step in a HAZOP is to identify the normal operating condition or purpose of the process or unit. This is called the intention, Next, a guide word is used to identity a possible deviation in the process. For example, the intention may be to keep the tempera- ture in a vessel constant. The guide words are * None, no, or not * More of + Less of ‘© More than or As well as * Partof * Reverse * Other than In the example here, there may be no coolant flow. Once such a possible deviation is identified, the team notes any possible amuses of the deviation. If there are any safety conse- quences of the deviation, those are noted. Suppose the coolant flow ceased because of a pump failure, The consequence may be a runaway reaction. The action to be taken is assigned by the HAZOP team. In this case, the action might be assigning the process engi- reer to investigate a backup pumping system. The team then goes on to the next possible deviation, until all reasonable deviations have been considered. The team does not solve the safety problem during the 1TAZOP; its job is to identify the problem and to assign its resolution to a specific person. An example of part of a HAZOP for the feed heater (E10!) of the hydrodealkylation of toluene process (Figure 1.5) is shown in Table 26.5, Several fea, tures of a HAZOP are shown. Several of the items are dismissed for “no probable cause.” Others are redundant. A few are outside-the-box deviations that could lead to important safeguards for rare events. Also, the result of the HAZOP is a list of action items. These action items are not themselves decisions to change the process. They are decisions 10 study potential changes. ‘The OSHA process safety management regulation requires that the actions assigned be taken in a timely manner and that all process hazard analyses be updated at least every five years(ag) 3 Fuveng aaeoqur “Simp sienmpamqoy spe souoseq aul joamyeradway posearny —_amyeraduan aie t co) vo waned jpromssang ampeyeqn, —aeppoqq ureansnog amscond mn t nor ny ayexnog 9 uang ‘wo poqso saps.) sieqroso10pey ——wrtoRIMparuappng ——_amyuodumn ese t sexy ——_uoperedo ajensun TorDve ut OD spnpoid wogenquo meade ‘og aoN PER peumqUA —ompEATETEOF PRE uo on ' nos 8 ny s22yr910 Yo sPoyrORIT Ue sapysuOD OCH MPM aur ur aBexoorg (ravens) mo on, voy wuenberuoy ane wonevea —_plOm erin (3.009 38 (9 ureang) s0y>¥az BYR 03 Paes 2ptaoad oF AK eremdig saieop poor TOL-T1 aman ssm20%g ss82044 (VGH) WORE RepOsPAH up 40 49}20H POD eI. 10} dOZVH $°9% >IEL1 “wBisep rejsnaep ysngoy, “aTpea aIRA98 LOHLOYY -yuetd yo oro Aosiaredns savamomy “MOE Mo 30 amssoxd sno] wo UEEY “unopinys pue were soe Tenwazopmp Yates powEHL ‘peo ‘woRSiar yr woRDSap ‘sumep oneuo;ne apny>uT “aA uopniac on vwopoaiep au apewoIny ? pen sounooeq au sureyd o woponinseq, scxbo ON Tor aoe > osenen py pe anode wos uuogoear Sunpuonb “TOT 013048 PIOD, ampaur aatsoydig pry some, guvang wramyeroduray soy 2OT-AJ0 moreso axrun, ‘neo ayqeqosd on, sastuep Tor-Asoamyer opeuzoy, ux01g aasdn sse201g, umansumop edidysing sang saqna year smoauety ‘suey ON oper seen We ooo aneumy yo 6507] t 8 very et sdosp prnbyr t amesosd seoydsouye Seo] sno 98 yong sqm vuramssoud $69] Purang ur umn 9 ‘uma WE Mop 927] amqeredura 0] 4 : = 3 3 4 34 2 28 souenbasuey esne POM PEND) (Panugquag) sserorg (vaH) voReV}eeposphy aut 40 12729 PREY BYR 104 JOZVH $°92 A1T@L“sampooord simp jo wounSeuow sag, “enneey a8ez0}8 wo sjox3409 seowaSeuets paepunpoy ‘somaezadunay 197-43 pue ‘SuoTES}UADUIOD JONUOPY “ord sossaidizoo ands upeureyy ‘zuvans vo mere Mog-mo] reso wopordeg snpoid peaotprueiat uoneaoeop wien 0/pur spnpordursonnday 08 on5 op warp 30 sq, uP LoLaro Ho ont suomoruatompa TOL-U UT uoRse= ON, ‘voRmppow ud Sump ‘uooeuu00 #u0%44 aBejoqes 49 TOTAL s2qny ur Suproqiase 30 pooy uy soma, ‘ene aqgeqnd on, -asneo ayqegord oN, Bupaom your 191 Buppom you LordSection V_ The Impact of Chemical Engineering Design on Society 26.4.2 Dow Fire & Explosion Index and Chemical Exposure Index ‘The Dow Fire & Explosion Index was developed by Dow Chemical in the 1960s and is today used by many companies to identify high-risk systems. It isa form of process ha ards analysis that focuses on fires or explosions, but it also goes beyond the identification of these hazards to quantifying the probable loss from a resulting fire or explosion. ‘The format of this index is similar in many ways to an income tax form, a8 seen in Figures 26.1 and 26,2, which are for a fictitious reactor in a polymer plant (provided by Dow Chemical, Inc,, May 1998, at a workshop for faculty). The details of these procedures are given in the official guide, available from AICHE [10]. First a specific process unit is selected. The components in the unit have the greatest impact on the hazard, so a “material factor” is determined. This factor is a measure of the energy released during a fire or explosion involving a specific material and varies from 1 (eg, for sulfur dioxide) to 40 (eg, for nitromethane). Material factors for 328 materials (substances or defined mixtures) are given in the official guide, as well as procedures for determining the factor for any other matetial based on flammability and reactivity. In the ‘case of the hypothetical example, the reactor contains several materials, but the material {factor for butadiene is the highest, soit is used as the base. Various corrections are made for type of reaction, facility, and materials handling to arrive at a general process hazards factor. In the case of Figure 26.1, there is a polymer- ization (exothermic) penalty, and there is a drainage and spill control penalty because there is only a 20-minute supply of fire water available. ‘Then a special process hazards factor is calculated based on extreme procese condi- tions, storage of large quantities of hazardous materials, corrosion and exosion, fired equi ‘ment, and so on. In the example, there isa toxic penalty of 0.4 for butadiene. The operation is nitrogen padded but operates in the flammable rangp, so a penalty of 0.3 applies. There is 0.06 penalty based on high-pressure operation with the specified relief setting, The flam- ‘mable material penalty is based on the total heat of combustion for all materials in the nit (aot only the butadiene). Corrosion has been estimated at less than 0.127 mm/y, and minor leakage at pumps occuts, which lead to the respective penalties. There is an agitator, which accounts for the rotating equipment penalty. From these three hazards indicators (materials factor, general process hazards factor, ‘and special process hazards factor), the Fire & Explosion Index (F&EI) is calculated, 169 in the example, Table 26 6 shows the qualitative level of hazard for various valses ofthe F&EL. ‘This example is in the “severe” hazard class, Although the F&EI is useful in identifying ‘process units where hazardous conditions exist, itcloes not estimate the damage that might result from such an event. The second part of the analysis (Figure 26.2) involves estimating the probable dam- age if the hazard leads to a catastrophic event. The damage from a fire or explasion depends on the area affected by the event, the value of the equipment destroyed, and the Table 26.6 Dow Fire & Explosion Index [10] Fire & Explosion Indox ‘Qualitative Hazard Level 10 61-96 or-27 128-158 159- Light Moderate Intermediate Heavy SevereChapter 26 Health, Safety, and the Environment FIRE & EXPLOSION INDEX Frnt con a JPstsimin facto [aa are —— $$ rsacaomasreng ——~ ler aasprsarca ‘aig [enee wight Sao [Cyetobexane, isopentane, DF, isoprene, Stren, Butane, PA, Phosphor Acid st er Krsna ny ‘econ Meterel Facto niet aren eee cavapoan one 2a fF Gated reese nae eee cee a ay nar aio . Ensood or incr Pros Unis ‘esses ied Aso Pasar) a don hor Now Fale Fangs 1. Tank Fans Soge vnate Ug | 2 Press psa or Pang fanaa 3a amined oa 0. Geant of Fama aTDRS Wie $. Uo Geant nace Goo Fae] —LisowP STU Li of Gases h Soaps (Sa Fg im Sbrape, busin Poca es Fa a [Spatial Proceas Hacards Factor) 02 [Process Unit Hazards Factor (Fx F,) =F; Tot Figure 26.1. Dow Fite é Explosion Index (Form reproduced with per- ‘ison of the American Insitute of Chemical Engineers. Copyright © 1994 AICHE. All rights reserved. Example used by permission of SACHE (www.aiche.org/sache), a component of the Center for Chemie cal Process Safety providing instructional materials to member chemical ‘engineering departments throughout the world )LOSS CONTROL CREDIT FACTORS 44 Procese Conttl Cod Factor; Section V_ The Impact of Chemical Engineering Design on Society SEE] cca exon oe fei feos ranngo__| Ree | Soe fas i Legit —f anit | Set re a = cota ofa remararciral esteealt ear Pe ee ereeat ie fsa af ae See rar {esteem ear Eseeeoe ose ae o,vaunel_—E—] issue nso) ase weir) oa | toe Tae | coe mre —__| age _| te a Seen Letras ea ote [eet a aes sre as So | Reece cms SS ccm = oor mee oe reuwrs | Rowe | Set a rel eee | reaabtet —t Ba Pro ee ae ee See on fen eam — fee oe ieee csvaueol ze] Loss Control Ged Factor«G,x0:x0,8)+[— 051] toronto 7 so PROCESS UNIT RISK ANALYSIS SUMMARY Prana Batt a = a ee soa eee a rs Sere poked TS aaa ey Sag aA | ee ae oI "2 Forno eral lac aloe 105, Frode Tat Tasos weed Tine to Fr & Exxoston index Hazard Castieaton Que fox deta Figure 26.2 Loss Control Credit Factors (Form zeprodced with per- mission of the American Institute of Chemical Engineers. Copyright © JOM AICHE. All rights reserved. Fxample used by permission of SACHE (wrwwaicheorg/sache), a component of the Center for Chemi- ‘al Process Safety providing instructional materials to member chemical engineering departments throughout the world.)Chapter 26. Health, Safety, and the Environment. 909 26.5 26.6

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