United States Environmental Protection Agency Hazardous Waste Engineering Research Laboratory Cincinnati OH 45268 Research and Development EPA/600/S2-87/068 Feb. 1988 &ERA Project Summary Manual for Preventing Spills of Hazardous Substances at Fixed Facilities Walter Unterberg, Robert W. Melvold, Kathleen S. Roos, and Patricia A. Scofield The purpose of this project was to prepare a manual that provides guidance on preventing spills of hazardous sub- stances in fixed facilities that produce substances from raw or starter mate- rials, store the substances, or transfer the substances to and from transporta- tion terminals. The emphasis is on smaller-sized chemical manufacturing facilities. The manual consists of seven sections and an Appendix: 1. Introduction; 2. Manual of Practice; 3. Hazardous Sub- stances and Their Characteristics; 4. Fixed Facilities; 5. Facility Spill Preven- tion Practices; 6. Preventive Engineering Practices; and 7. Bibliography. The appendix contains descriptions of fixed facility chemical processing equipment components, from which a checklist of equipment items interacting with hazardous substances can be derived for use in preparing a Spill Prevention Plan. This Project Summary was developed by EPA's Hazardous Waste Engineering Research Laboratory, Cincinnati, OH, to announce key findings of the research protect that If fully documented In a separate report of the same title (see Project Report ordering Information at back). Introduction The purpose of this project was to prepare a manual that provides guidance on preventing spills of hazardous sub- stances from fixed facilities that produce hazardous substances from raw or starter materials as products, byproducts or waste products; store hazardous sub- stances; or transport hazardous sub- stances. The audience to be addressed includes managerial and supervisory personnel as well as "hands on" per- sonnel associated with smaller-sized chemical manufacturing facilities. The hazardous substances in question num- ber almost 700, excluding oil, and are those designated pursuant to Section 101 (14) of the Comprehensive Environmental Response, Compensation and Liability Act of 1980, otherwise known as CERCLA or Superfund (Public Law 96-510). The earlier Clean Water Acf (Public Law 92-500) in Section 311, required that the President issue regulations "establishing procedures, methods and equipment ... to prevent discharges of oil and hazardous substances from vessels and from onshore and offshore facilities..." Under a 1973 executive order, the U.S. Environmental Protection Agency (EPA) was to promulgate regula- tions for preventing nontransportation- related spills. In 1973, EPA issued oil pollution pre- vention regulations (40 CFR Part 112) that require certain fixed facilities to have on file a spill prevention, control and countermeasures plan (SPCC plan). These regulations have been largely accepted by industry and have proven to be effective in preventing oil spills. In the case of hazardous substances, no similar federal regulations exist at this time. In its own interest, a large segment of the industry producing, storing, and handling hazardous substances has in- stituted internal spill prevention plans. However, many of the smaller affected facilities may not have generated spill prevention plans for various reasons. This manual is designed to assist them in preparing such plans. ------- <*! Source material for this manual was derived from government, industry and commercial publications. Related oil spill prevention literature included: the Guide for Inspectors; a report on Prevention Practices at Small Petroleum Facilities; state contingency plans, such as the Oil Spill Contingency Plan of the State of California; and the extensive Oil Spill Prevention Control and Countermeasure Plan Review. Publications dealing with hazardous substances included cost analyses for hazardous substance pollu- tion prevention, Best Management Prac- tices (BMP) documents, an industrial spill prevention plan, and a treatise on Safety and Accident Prevention in Chemical Operations. Manual of Practice Section 2 of the manual presents the procedure for developing a facility spill prevention master plan. The procedure is divided into 10 steps that are expanded in the remainder of the manual. The manager selected to oversee the plan, and constant support of upper level management, are essential for successful implementation of the project. Specialists, as required to perform the various tasks outlined below, and the involvement of people from different parts of the facility, will provide a wide base of support for the plan and increase its acceptance by plant personnel who will be its main beneficiaries. The 10 procedural steps are as follows: 1. Form a facility spill prevention organization supervised by a part- time or full-time manager and backed by the plant management. 2. Prepare a prevention policy state- ment approved by management. 3. Define facility boundaries and pre- pare flowsheets indicating genera- tion and storage of all substances within these boundaries, as well as inflow and outflow of substances across the boundaries. Hazardous substances present in raw materials, products, byproducts, wastes, fuels, lubes, paints, pesticides, disinfec- tants, etc., should be identified. Normal and overload conditions should be noted. 4. List the substances that are hazard- ous by reference to Section 3 and the tables of hazardous substance characteristics contained therein. Note the environmental media into which the substances would be released, their physical behavior on release, and the hazards caused by the release. 5. List all facility areas and equipment items that interact with hazardous substances. Include storage vessels of all kinds (gas, liquid, solid), process vessels and columns, flow systems including valves and controls, re- ceiving and shipping terminals of all kinds (road, rail, water, air), and waste treatment and disposal areas. Use Section 4, Fixed Facilities, to identify those areas and equipment that could interact with hazardous substances. 6. For each area and equipment item of interest, list possible failure modes; amount of hazardous sub- stance involved; hazards caused by possible release of substance (from Step 4 above); and specific effects expected on the rest of the facility and surroundings, considering equipment and personnel at various times and varying weather con- ditions. 7. For each area and equipment item, look over Section 5, Facility Spill Prevention Practices (SPPs), and extract the applicable Preventive Engineering Practices. 8. For each area and equipment item, look over Section 6, Preventive Engineering Practices (PEPs), and extract the applicable PEPs. 9. Write a facility spill prevention master plan under direction of the manager by combining information from Steps 3 through 8. The plan should consider drainage to receiving waters and facility terrain, and should include a timetable for carry- ing out the SPPs and PEPs. 10. Have the plan approved by plant management and implemented under direction of the spill prevention organization, which also should be responsible for its periodic review and revision. Hazardous Substances and Their Characteristics Section 3 of the manual contains tables of information on the almost 700 CERCLA-designated hazardous sub- stances. Once all the substances within a plant have been identified, they should be checked against these tables to deter- mine which are hazardous. Only those considered hazardous require further consideration. Hazardous substances may be gases, liquids, or solids; and, they may be re- leased to the air, water, or ground. The manual presents four tables: (1) liquids and solids spilled on water, (2) liquids I spilled on ground, (3) solids (particulates) released to air or ground, and (4) gases released to air (a sample page from each is provided here as Tables 1 -4, re- spectively). Table 1 contains (1) an alphabetical listing of substances, primarily chemical compounds; (2) chemical class, some- times more than one; (3) Chemical Abstract Service (CAS) number, a stan- dard in cases where substances are known by more than one name; (4) hazards in addition to toxicity; and (5) behavior in water — sink/float and soluble/insoluble. The fifth or last column, "Behavior in Water," is not included in Tables 2, 3, and 4. The hazards listed in the fourth column of each table are defined in 49 CFR 173 (Department of Transportation (DOT) regulations), the Clean Water Act, and by the U.S. Department of Health and Human Services. In the following list, an asterisk designates definitions developed during this work. • Carcinogen — substance identified as potentially cancer-producing in humans. • Combustible — liquid or solid having a flash point at or above 100°F and below 300°F; the upper limit was changed from the DOT value of 200°F to 300°F to realistically in- clude more substances as com- bustible. • Corrosive — substance causing visible destruction or irreversible alterations in human skin tissue at the site of contact. • Explosive — any chemical compound, mixture, or device providing sub- stantial instantaneous release of gas and heat. • Flammable — substance as defined in 49 CFR 173.300 (gas), 49 CFR 173.115 (liquid), and 49 CFR 173.150 (solid). • Oxidizer — substance that yields oxygen readily to stimulate the combustion of organic matter. • Poison — substance so classed or labelled in 49 CFR 172.101. • Polymerizable — substance under- going a rapid exothermic polymeriza- tion reaction initiated by exposure tc heat, light, acids, caustics, or othei sources. • Radioactive material — substanct spontaneously emitting ionizing radiation. • Reactive — substance that readily undergoes violent change withou ------- Table 1. Releases in Water Hazardous Substance Acenaphthene Acenaphthylene Acetaldehyde Acetic acid Acetic anhydride Chemical Class Aromatics Aromatics Aldehydes Acidic compounds, organic Acidic compounds, organic CAS No. 83-32-9 208-96-8 75-07-O 64-19-7 108-24-7 Hazardts). in Addition to Toxicity Combustible Combustible Flammable Polymerizable Combustible Corrosive Combustible Corrosive Behavior in Water Insoluble Sinker Insoluble Floater Soluble Soluble Soluble, decomposes Acetone Acetone cyanohydrin Acetonitrile Acetophenone Acetyl bromide Acetyl chloride 2 -A cetylaminofluorene 1 -Acetyl-2-thiourea Acrolein Aery I amide Ketones Cyanides and nitrites Cyanides and nitrites Ketones Aliphatics, halogenated Aliphatics, halogenated Amines, aryl Ureas Aldehydes, Olefins Amides, anilides, and imides 67-64-1 Flammable 75-86-5 Combustible w/toxic products Poison 75-05-8 Flammable w/toxic products 98-86-2 Combustible 506-96-7 Flammable w/toxic products Corrosive Reactive 75-36-5 Flammable w/toxic products Corrosive Reactive 53-96-3 Potential carcinogen 591-08-2 107-02-8 Flammable Polymerizable Poison 79-O6-1 Polymerizable Soluble Soluble Soluble Insoluble Sinker Decomposes (Sinker) Decomposes (Sinker) Insoluble Sinker Soluble Soluble Solubit detonation in the presence of water or moist air, or even dry air or oxygen. • Toxic pollutant — material which upon exposure, ingestion, inhalation, or assimilation into any organism, causes death, disease, behavioral abnormalities, cancer, genetic muta- tions, physiological malfunctions, or physical deformations. A thorough understanding of the various hazards is essential for effective selection of preventive countermeasures. This sec- tion provides data in the form of four tables of Hazardous Substance Charac- teristics for identifying and listing those substances that are hazardous in ac- cordance with Step 4 of the procedures for developing a facility spill prevention master plan. The first page of each of the following tables is presented as a sample. Table # Release Scenario 1 Releases in Water 2 Liquids Released on Land 3 Paniculate Solids Released on Land 4 Compressed Gases Released Into A ir Fixed Facilities The manual can be applied to any fixed facility. If one excludes the petroleum refining industry, which is covered by an existing Oil Pollution Prevention Regula- tion (40 CFR 112), there are 20 major industry categories defined in 40 CFR 124, Appendix D, as follows: No. Major Industry Category 1 Timber Products Processing 2 Steam Electric Power Plants 3 Leather and Leather Products 4 Iron and Steel Manufacturing 5 Inorganic Chemicals Manufacturing 6 Textile Mills 7 Organic Chemicals Manufacturing 8 Nonferrous Metals Manufacturing 9 Paving and Roofing Materials 10 Paint and Ink Formulation and Printing 11 Soap and Detergent Manufacturing 12 Auto Wash and Other Laundries 13 Plastics and Synthetic Metals Manufacturing 14 Pulp, Paper and Board Mills, and Products Manufacturing 15 Rubber Processing 16 Miscellaneous Chemicals 17 Machinery and Mechanical Products Manufacturing 18 Electroplating 19 Ore Mining and Dressing 20 Coal Mining Several of these categories fall within the chemical manufacturing area. Others, ------- Table 2. Liquids Released on Land Hazardous Substance Acetaldehyde Acetic acid Acetic anhydride Chemical Class Aldehydes Acidic compounds, organic Acidic compounds, organic CAS No. 75-07-0 64- 1 9-7 108-24-7 Hazardfsj, in Addition to Toxicity Flammable Polymerizable Combustible Corrosive Combustible Corrosive Acetone Ketones Acetone cyanohydrin Cyanides and nitrites Acetonitrile Acetophenone Acety/bromide Acetyl chloride Acrolein Acrylic acid Acrylonitrile Ally! alcohol Cyanides and nitrites Ketones t," ;*,•<>, halogenated Aliphatics, halogenated Aldehydes, Olefins Acidic compounds, organic, Olefins Cyanides and nitrites Alcohols andglycols, Olefins 67-64-1 Flammable 75-86-5 Combustible w/toxic products Poison 75-O5-8 Flammable w/toxic products 98-86-2 Combustible 506-96-7 Flammable w/toxic products Corrosive Reactive 75-36-5 Flammable w/toxic products Corrosive Reactive 107-02-8 Flammable Polymerizable 79-10-7 Combustible Corrosive Polymerizable 107-13-1 Flammable w/toxic products Polymerizable Potential carcinogen Poison 107-18-6 Flammable Poison such as mining (Nos. 19 and 20), metal processing in various forms (Nos. 4, 8, 18, and 19), and production of non- metal lies (Nos. 3, 6, 9, 13, 14, and 15), also deal with hazardous substances. Each industry has its own specialized equipment and facility areas. For the present purpose, this section lists and describes the equipment found in chemi- cal manufacturing plants. For other in- dustries, this section and the Appendix would have to be modified. In accordance with Step 5 of the procedures for preparing a master plan, a list of plant component interactions with hazardous substances is required. A check list of all facility areas and components is useful for developing the final list. Reference to the Chemical Engineers' Handbook (1973, 5th edition) led to the identification of major facility area categories which cover processing, transportation, storage, waste treatment, and disposal. A detailed description of hazardous substance interactive systems and equipment (including further division of the major categories) is provided in the Appendix. A listing of the systems and equipment is provided here: 1. Transport and storage of fluids (pumps, pipes, valves, tanks, etc.) 2. Handling of bulk and packaged solids (conveyors, silos, etc.) 3. Size reduction and enlargement (mills, compactors, etc.) 4. Heat generation and transport (fired process equipment, incinerators, etc.) 5. Heat transfer equipment (heat ex- changers, condensers, etc.) 6. Evaporative cooling and refrigera- tion (cooling towers, cryogens, etc.) 7. Distillation columns 8. Gas absorption towers 9. Liquid extraction systems 10. Adsorption and ion exchange equipment 11. Miscellaneous separation pro- cesses (crystallization, membranes, etc.) 12. Liquid-gas systems (contacting, phase dispersion, phase separation) 13. Liquid-solid systems (contacting, phase dispersion, phase separation) 14. Gas-solid systems (contacting, phase dispersion, phase separation) 15. Liquid-liquid systems (contacting, phase dispersion, phase separation) 16. Solid-solid systems (contacting, phase dispersion, phase separation) 17. Waste treatment plants (equip- ment associated with primary, secondary, and tertiary treatment and disposal). Facility Spill Prevention Practices In general, spill prevention practices (SPPs) are independent of the exact nature of the facility, its processes and products. While most SPPs are based on common sense and experience and provide few new revelations, it is useful to have this compilation of procedures when preparing a spill prevention master plan. SPPs have been drawn from govern- ment and industry reports and publica- tions. Some, listed here, overlap into related areas such as response to a spill, maintenance, and training. If the facility already has plans and procedures in these areas, they can be adapted to the present purpose. A short discussion for each SPF listed below is given in the manual. SPILL PREVENTION ORGANIZATIOls RISK IDENTIFICATION AND ASSESSMENT MATERIALS COMPATIBILITY REPORTING AND RECORDKEEPINC GOOD HOUSEKEEPING PREVENTIVE MAINTENANCE INSPECTION SYSTEMS SECURITY EMPLOYEE TRAINING ------- Table 3. Paniculate Solids Released on Land Hazardous Substance Chemical Class CAS No. HazardfsJ, in . Addition to Toxicity Acenaphthene Acenaphthylene 2-Acetylaminofluorene 1 -Acetyl-2-thiourea Aery/amide Aromatics Aromatics Amines, aryl Ureas Amides, anilides and imides 83-32-9 208-96-8 53-96-3 591-08-2 79-06-1 Combustible Combustible Potential carcinogen Polymerizable Adipic acid Aldicarb Aldrin Aluminum phosphide Aluminum suit ate S-fAminomethyll-3- isoxazolol Amitrole Ammonium acetate Ammonium benzoate Ammonium bicarbonate Acidic compounds, organic Esters Aromatics, halogenated Phosphorous and compounds Sulfates Amine, alkyl Azo compounds Organic ammonium compounds Organic ammonium compounds Organic ammonium compounds 124-04-9 116-O6-3 309-00-2 Combustible w/toxic products Potential carcinogen Poison 20859-73-8 Flammable w/toxic products Reactive 10043-01-3 2763-96-4 61-82-5 Potential carcinogen 631-61-8 Ammonium bichromate Chromates 1863-63-4 Combustible w/toxic products 1066-33-7 7789-O9-5 Corrosive Oxidizer Flammable Preventive Engineering Practices Preventive engineering practices (PEPs) may be thought of as SPPs that are oriented toward equipment rather than procedures. They are specific to groups of toxic and hazardous substances and to the potential sources of spill, that is: storage areas; loading/unloading areas; inpfant transfer, process and materials- handling areas; drainage from plant site and secondary containment structures; and waste storage, treatment and disposal facilities. PEPs are divided into pre-release and post-release groups, both designed to confine release within the facility bound- aries. The difference between the two is that pre-release PEPs are of a general precautionary nature, whereas post- release PEPs are activated as spill control devices by a release. Typical pre-release PEPs include monitoring and alarm sys- tems, non-destructive testing, labeling all storage, process and flow equipment, and proper storage procedures. Typical post- release PEPs include secondary contain- ment of liquids and solids by dikes and berms, flow diversion, vapor control, and dust control. The manual discusses the following subsections (grouped by equipment cate- gories, emphasizing components found in chemical manufacturing facilities). • Bulk Storage Tank Construction Tank Support Tank Placement Tank Monitoring Material Storage Alarms Fire Protection Systems Secondary Containment • Loading and Unloading Areas Tank Truck Loading/Unloading Railroad Tank Car Loading/Unloading Marine Loading/Unloading • In-Plant Process and Transfer Process Materials/Equipment Instrumentation Piping Valving Venting Color Coding/Labeling • Drainage Control Facility Diking Road Drainage Plant Drainage Drainage Valving Secondary Containment • Waste Storage, Treatment and/or Disposal. Appendices The manual includes the following appendices: • Fixed Facility Chemical Process Equipment Components Transport and Storage of Fluids Handling of Bulk and Packaged Solids Size Reduction/Enlargement Heat Generation and Transport Heat Transfer Equipment Evaporative Cooling and Refrigeration Distillation Columns Gas Absorptive Towers Liquid Extractive Systems Adsorption and Ion Exchange Equipment Miscellaneous Separation Processes Liquid-Gas Systems Liquid-Solid Systems Gas-Solid Systems Liquid-Liquid Systems Solid-Solid Systems Waste Treatment Plants ------- Tab/* 4. Compressed Gases Released Into Air Hazardous Substance Chemical Class Hazardfs), in CAS No. Addition to Toxicity Ammonia Carbon oxyfluoride Chlorine Cyanogen Ammonia Halides, alkyl Halogens Cyanides and nitrites Dichlorodifluoromethane Halides, alkyl Dimethylamine Amines, alkyl Fluorine Formaldehyde Hydrogen sulfide Methyl bromide Methyl chloride Methyl mercaptan Nitric oxide Phosgene Halogens Halides, alkyl Halides, alkyl Monomethylamine Amines, alkyl 7664-41-7 353-50-4 7782-50-5 460-19-5 75-71-8 124-40-3 7782-41-4 Aldehydes 50-00-0 Sulfides and mercaptans 7783-06-4 74-83-9 74-87-3 Sulfides and mercaptans 74 -S3 -1 Oxides Halides, organic 74-89-5 10102-43-9 75-44-5 Corrosive Reactive Oxidizer Poison Flammable w/toxic products Poison Flammable w/toxic products Corrosive Corrosive Reactive Oxidizer Poison Flammable Flammable w/toxic products Poison Combustible w/toxic products Poison Flammable w/toxic products Flammable w/toxic products Corrosive Flammable w/toxic products Corrosive Poison Oxidizer Combustible w/toxic products Poison ------- ------- Walter Unterberg. Robert W. Me/volet, Kathleen S. Roos, and Patricia A. Scofield are with Combustion Engineering, Environmental Monitoring Services. Inc., NewburyPark, CA 91320. Leo T. McCarthy (deceased) was the EPA Project Officer (see below for present contact). The complete report, entitled "Manual for Preventing Spills of Hazardous Substances at Fixed Facilities," (Order No. PB 87-232 815/AS; Cost: $18.95. subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 John S. Farlow can be contacted at: Releases Control Branch Hazardous Waste Engineering Research Laboratory—Cincinnati U.S. Environmental Protection Agency Edison, NJ 08837 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES P> EPA PERMIT No G-35 Official Business Penalty for Private Use $300 EPA/600/S2-87/068 0000329 PS U S E«VIR I»ROTECT10R AGENCT RC610W 5 I"****™ Z30 S D6ARBS8K STREET CWICA60 It $0604 ------- |