Document RpQjk7ap8ZokogdYEMzeJojav

23 September 1985 Members of the Vinyl Institute Manufacturing Practices Committee Enclosed you will find two Items, as discussed at the Tampa meeting: 1) Draft comments to EPA on the proposal to Install stripping or other pretreatment ahead of the biological system at OCPSF plants. Please review this promptly and send duplicate comments to me and Peter de la Cruz so as to arrive before 9 October. We expect a delay In the present 15 October comment deadline, but want to be prepared If It Is not allowed. 2) A copy of a portion of a draft MSDS for vinyl chloride (the storage section) prepared In 1976 by R. N. Wheeler, et al. It'was Intended to be used by CMA, who stopped Issuing safety data at about that time. It Is requested that you, or whomever else may be your representative to the Safety Subcommittee, review this document to see If It could be a vehicle for starting the preparation of a VC storage practice guideline. The most useful form of reply would be a marked up copy of the document, and/or an outline of a proposed new document. New sections that are needed, and errors In this document should receive particular attention. Please let me have a reply before 16 December. Roy Is sending out letters to your VI Board Members this week soliciting nominations for the 1986 Safety Award. You voted to continue the award. Please send In nominations. Thanks for your help. JTB:cb 0121c/CSB Attachments BOR 012136 Air Products and Chemicals, Inc. Box 538 Allentown, PA 18105 Telephone (215j 481-4911 AIR -A PRODUCTS 1; 23 September 1985 Hr. E. H. Forsht Industrial Technology Division (WH-552) US EPA 401 M Street, S.W. Washington, D.C. 20460 Attn: ITD Docket Clerk OCPSF Rules Dear Mr. Forsht: The Vinyl Institute, a division of the Society of the Plastics Industries, Inc., provides as requested comments on the new Issues raised In the OCPSF effluent guideline rulemaking In a notice at 50 FR 29069, 17 July 1985. Our comments are directed particularly at the proposal to Institute In-plant stripping requirements for vinyl chloride and 1,2-dlchloroethane, but we believe that the principles discussed here are applicable to the entire question of In-plant control technologies that require non-blologlcal pretreatment. We oppose these additional requirements because we find no authority for such requirements In the Clean Water Act, and because we find no data In the Notice providing a reason for believing that there may be a health-based benefit for such requirements. Insert SRI/VI boiler plate here. I. The Agency has no authority for the proposed action. There Is no recitation of authority In this Notice. The previous proposal (48 FR 11828, 21 March 1983) cited the Clean Water Act as Its basis for the authority to develop and enforce this rule, so that, presumably, Is the authority being relied on In this continuation of that rulemaking. Nowhere In the Clean Water Act Is there authority for the Agency to base Its decisions on air quality. Title III of that Act, and more specifically Sec. 307, which discusses the setting of effluent standards for toxic substances, recite only water quality criteria which the Administrator Is to consider In setting the effluent standards. Air quality considerations are not Included. BOR 012137 Page 2 23 September 1985 We therefore believe that the Agency Is acting without authority when It proposes that effluent guidelines shall contain provisions that are related solely to air quality, and have no effect on water quality. It Is pointed out In Tables 0-1 and D-2 that the effluent concentration of 1,2-dlchloroethane Is expected to be lower (10 ppb nominal, or actually, non-detectable) under Option I, (Table 0-1) which uses biological treatment only than Is to be (13.4 ppb) under Option II (Table 0-2) which uses biological treatment plus In-plant pretreatment. Thus, the agency figures suggest that the proposed pretreatment would actually be counterproductive Insofar as lowering the amount of 1,2-dlchloroethane which would be discharged to the waterways. II. There Is no health or environmental benefit proposed for this requirement. Executive orders 12291 and 12498 require that every regulation show some net positive benefit. In addition to the basic requirements that It be needed In the first place, and Is responsive to that need. This proposal fails all three of those tests. No need Is shown for the reduction claimed to occur because of this added requirement, nor Is any benefit shown. The proposal thus Is In direct violation of the two Orders cited above. The Agency already has a very strict NESHAP rule for vinyl chloride which regulates strictly the emissions from both air and water by ethylene dlchlorlde/vlnyl chloride producers and processors. The Agency recently has reevaluated the rule, and concluded that the major portions, Including the process emission controls* provide adequate protection to the public. See 50 CFR 1182, 9 January 1985. The Agency currently Is defending vigorously Its authority to hold to the current standard, particularly In regard to the lack of necessity to lower the current emission standard. See the pleadings In NR0C v. EPA, et al., 85-1150, D.C. Circuit. It Is the Agency's position In that case that the current standard Is adequate, and that no further reductions are justified. Therefore, we can see no basis for another Office of the Agency to attempt to contradict the official Agency position and attempt to Impose further restrictions on emissions of vinyl chloride. BOR 0l2l38 Page 3 23 September 1985 A preliminary estimate of the vinyl chloride released as effluent emissions from a world-scale (300 MM Ib/yr) PVC plant shows a receptor concentration of less than 0.1 ppb at one-fourth of a mile from the effluent treatment area, at a 1 mph wind speed. This concentration Is so low that conventional dispersion models have difficulty predicting the results. That part per trillion value certainly Is not a concentration which elicits significant health or environmental concerns. We are aware of the recent "6-Month Study* which led to a complete overhaul of the Agency air toxic policy last June. We also are aware of the many caveats and conditions warning against literal acceptance of the results which were expressed In that report. Dr. Bernard Goldstein, the Immediate past Assistant Administrator for Research and Development, has called these risk estimates "speculative". However accurate the quantitative aspects may be, the study found that Industrial emissions were of far less concern than products of Incomplete combustion from automobiles and home heating systems, and of even less concern than airborne chromium dusts, and other minor pollution sources. Even If air emissions from Industrial sources were of overall concern to the Agency, which the Agency has said they are not, effluent-based emissions are only a minor part, and are. In the long run, not subject to regulation by a Clean Water Act effluent guideline. We appreciate the opportunity to provide comments on this matter. As stated earlier, we believe that the principles here apply to the pretreatment proposal In general, and we have utilized the vinyl chloride case as Illustrative. We would be happy to provide further Information on any of these points If that should be desirable. We request strongly that the Water Office consult with the Office of Air Quality Planning and Standards to obtain further Insight Into their positions regarding the air toxic problem. Very truly yours, JTB:cb 0118C/CSB BOR 012X39 Section 8 SHIPPING, LABELING AND HANDLING 8.1 Storage 8.1.1 General Vinyl chloride storage areas should always be selected to comply with all applicable locai codes and regula tions, especially those involving occupational health, environmental control, hazardous materials and fire prevention. Organizations such as The National Fire Protection Association, The National Board of Fire Underwriters and the Factory Insurance Association can be consulted about proper site selection. 8.1.2 Conditions of Storage (A) Vinyl chloride is a very volatile, toxic and flammable gas at normal atmospheric conditions. Vinyl chloride may be stored for reasonable periods of time (one year) without danger from the hazardous decompo sition or polymerization of vinyl chloride when kept in contact with ferrous materials and in the absence of air, oxygen, water, light or excessive heat. Containers and vessels used for handling vinyl chloride at ambient temperatures are usually under pressure. Nitrogen blanketing may be employed to increase the storage pressure in order to facilitat"? tank pumping operations. Refrigeration can be used to maintain the storage temperature within an acceptable range - below 50 and preferably between 0C and 20C. Vinyl chloride, properly stored, uninhibited either under refrigeration or at normal atmospheric temperature, . should be checked regularly for the presence of polymers. (B) All piping, instrument leads, storage tanks, relief devices and other equipment employed to handle vinyl chloride should be constructed of recommended materials. (See Section 7.2) This equipment should be designed to withstand a full vacuum, if practical, or a working pressure of at least 100-150 psi conforming to the ASME code for unfired pressure vessels or any code applying to the locale of planned storage. Vapor recompression or refrigerated storage tanks can be designed, however, for lower operating pressures. Shut-off valves and control valves should be of steel or a suitable alloy not containing copper, and these valves should be designed for working pressures of at least 150 psi. All welded construction is recommended to insure a A-34 BOR 012140 8.1 Storage (continued) 8.1.2 Conditions of Storage (continued) leakproof integrity. Wherever po:;:ihlo, .ill .liquid inlet lines should enter the hot ton or extend to the bottom of the storage vessels. This contributes to the guarding against the accumulation of static elec tricity. All equipment should be properly grounded and bonded with resistance to ground never exceeding 25 ohms. The stand leg should have an opening in it near the top of the tank to act as a vacuum breaker and to help prevent blowback. All electrical wiring, lighting and equipment should comply with NEC require ments. Vinyl chloride tanks should be painted with white or other heat reflective paint. (C) All storage areas should have installed an appro priate water spray system or automatic sprinkling system or other special fire extinguishing systems which are suitable for use with Class B fires. Portable fire extinguishers of the carbon dioxide or dry chemical type should be readily accessible to personnel in these areas. (See Section 5) Diking and/or draining to a safe location should be pro vided in all storage areas to completely confine and dispose of the liquid in the event of a major spill or vessel rupture. 8.1.3 Isolation Vinyl chloride storage areas should be selected and constructed in accordance with local codes or author ties having jurisdiction. Such highly volatile and flammable materials should be stored outside of buildings. Pre ferably, vinyl chloride storage tanks should be segregated away from major process units. Process units such as furnaces or reactors, which have a higher than average fire or explosion risk potential, should be situated as far from such storaqe tanks as practical. All potential ignition sources should be eliminated from such storage areas. Cylinders containing vinyl chloride should be stored in a vertical position, outside of buildings and in an isolated and well ventilated area. It is best to store cylinders in the open, but provision should be made to shield them from the sun's direct rays and to prevent the accumulation of dirt, snow, water or ice on their valves or safety devices. Vinyl chloride storage areas should be restricted to authorized personnel only and are often classified as "regulated areas" per OSHA. A-35 BOR 012141 8.1 Storage (continued) 8.1.4 Regulatory Aspects (A) 20 CFR 1910.1017 outlines the scope, application and specific requirements of the Occupational Safety and Health Standard for Vinyl Chloride. Specific sections of this standard nrovide for per sonnel exposure limits, regulatinq areas to authorized individuals, environmental monitoring, respiratory pro tection, labeling, etc. A vinyl chloride program must be established and comply with all the requirements of 29 CFR 1919.1017. (B) 40 CFR Part 61 "The National Emission Standards for Hazardous Air Pollutants" outlines the rules and regulations governing vinyl chloride emissions that have been established by the Environmental Protection Agency. The provisions of this standard should be complied with by the owner or operator of a vinyl chloride plant. 8.1.5 Compatible and Dangerously Reactive Materials Vessels used for vinyl chloride should be ^..ly used for vinyl chloride. They must be purged with a dry inert gas until free of oxygen (-<1,000 ppm) prior to filling. VCM is generally non-corrosive at normal atmospheric temper atures when dry (moisture free). However, mild to appre ciable corrosion has been reported whc vinyl chloride is wet even at ordinary temperatures. This may be due to the presence of impurities. In contact witn water at elevated temperatures vinyl chloride accelerates corrosion of iron and steel. Acetylene as an impurity in viny\ chloride may form an explosive compound (acetylide) when exposed to copper or copper alloys. 8.2 Labeling and Identification The statements and items listed below summarize the major label ing requirements; however, they are not necessarily complete or comprehensive. It is recommended that the Federal Code of Regu lations be consulted for tdie specific details and labeling requirements of the Department of Transportation, OSHA and the Coast Guard. 8.2.1 Department of Transportation Requirements - Coast Guard. 8.2.1.1 Cylinder by Water, Land or Air 49 CFR 172.101 - Each container and overpacked cylinder containing vinyl chloride (including tank cars) shall carry a label "Flammable Gas" and a name "Vinyl Chloride" as shown on the outsid* of any shipping container and on any shipping papers. A-36 BOR 012142 8.2 Labeling and Identification (continued) 49 CFR 172-417 - Small cylinders should have a four-inch "Flammable Gas" label which is red in color and has black printing and cylinder marked with "Vinyl Chloride". 172.417 FLAMMABLE GAS label. (a) Except for size and color, the FLAMMABLE GAS label must be as follows; (b) In addition to complying with 172.407, the FLAMMABLE GAS label must be red. The printing and symbol must be black. 49 CFR 173-306 - Exceptions from Department of Labor label ing requirements. 49 CFR 172.400 - General labeling requirements, placement of labels. 49 CFR 172.326 - Any portable tank (cylinder) containing more than 1,000 pounds of vinyl chloride must be marked in letters two inches or more in size with the shipping name "Vinyl Chloride' and have the Flammable Gas label affixed. Any truck moving the portable vinyl chloride containing tank must be placarded on the two sides as well as front and rear with "Flammable Gas" placard. (Paragraph 172.515 and Appendix B) The square on the point placard should be made from tagboard and have a size 10 3/4" by 10 3/4". It should withstand thirty days open weather exposure. The letters on this placard should red in color with wh: te lettering. A-37 BOR 012143 8.2 Labeling and Identification (continued) 8.2.1.2 Barge in Bulk 46 CFR 151.45-2 (e) Cargo Signs and Cards. Warning signs shall be displayed on the vessel, port and starboard facing outward without obstructions at all times except when the vessel is gas free .... 46 CFR 151.45-7 Shipping Papers. Each barge carrying danger ous cargo shall have on board a bill of lading manifest or shipping document giving the shipper, loading point location and the kind, grade and approximate quantity by compartment of each cargo in the barge .... i 46 CFR 151.50-34 (h) The words "Cancer-Suspect Agent" must be added to the warning signs required by 46 CFR 151.45.2 (e) . 8.2.1.3 Ship in Bulk 46 CFR 35.30-1 (b) General Safety Rules. A sign shall be displayed to warn persons approaching the gangway while a vessel is moored or anchored unless it is empty and gas-freed. The sign shall state in letters not less than two inches high substantially as follows: WARNING NO OPEN LIGHTS NO SMOKING NO VISITORS 46 CFR 151.45-2 (e) 3 A cargo Information Card for each cargo regulated by this subchapter shall be carried on the bridge or in the pilot house of the towing vessel readily available for use by the person in charge of the watch .... 46 CFR 40.15-1 (b) and (c) The words "Cancer-Suspect Agent" must be added to the warning sign required by 46 CFR 35.30-1 (b) Signs bearing the legend: Cancer-Suspect Agent in This Area Protective Equipment Required Authorized Personnel Only must be posted whenever hazardous operations, such as tank cleaning, are in progress. 8.2.1.4 Portable Tanks. Portable tanks are not authorized for use with vinyl chloride. A-38 BOR 012144 8.2 Labeling and Identification (continued) 8.2.2 MCA Recommended Label 8.2.2.1 The Manufacturing Chemists Association recommends that all containers of vinyl chloride should bear a label as shown. The text of the label is designed for the product as shipped for industrial use. It should be used in addition to or in combination with any specific wording required by law. Since individual statutes, regulations or ordinances may require that particular information be included in a label, that certain information be displayed in a particular manner, or that a specific label be affixed to a container, the use of this label will not necessarily insure compliance with such laws. VINYL CHLORIDE DANGER! EXTREMELY FLAMMABLE LIQUID AND GAS UNDER PRESSURE HARMFUL IF INHALED MAY POLYMERIZE VIOLENTLY UNDER FIRE CONDITIONS OR LOSS OR REMOVAL OF INHIBITOR Keep away from heat, sparks, and open dome. Keep container closed. Use with adequate ventilation. Avoid breathing vapor. Avoid contnct with skin. Keep cylinder out of sun and away fiom lu:at. Container should be gioundcd when being emptied. Never drop cylinder, FIRST AID: If inhaled, remove to fresh air. If not breathing give artificial respiration, preferably moufh-to-moulh. If breathing is difficult, give oxygen Call a physician. In case of: Fire -- Use water spray, dty chemical, or CO . Spill or Leak For small spills, evacuate area and permit to evaporate, foi lui ge sjnils or leaks, evacuate uica. Dike or llu'.li la oiiiiirid am) let evapai ilie Do not flush to ewer Ih-< mum- uf |>I.I'.ion hazard. MCA Cltrnifciil Stiffly D iiio Sited SDS6 (ivcnloblc. A-39 BOR 012145 8.2 Labeling and Identification (continued) 8.2.3 OSHA Labeling Requirements 8.2.3.1 The Occupational Safety and Health Administration (OSHA) is authorized by the Occupational Safety and Health Act of 1970 to establish occupational safety and health standards. 29 CFR Part 1910.1017 lists all the requirements for the control of employee exposure to vinyl chloride. The re quirements of this health standard include environmental monitoring, the establishment of regulated areas, training and use of specific signs and labels. 8.2.3.2 Entrances to regulated areas* shall be prominently posted with legible signs bearing the legend: Cancer-Suspect Agent Area Authorized Personnel Only 8.2.3.3 Areas containing hazardous operations or where an emergency** currently exists shall be posted with legible signs bearing the legend: Cancer-Suspect Agent in This Area Protective Equipment Required Authorized Personnel Only 8.2.3.4 Containers of polyvinyl chloride resin waste from reactors or other waste contaminated with vinyl chloride shall be legibly labeled: Contaminated with Vinyl Chloride Cancer-Suspect Agent 8.2.3.5 Containers of polyvinyl chloride shall be legibly labeled: Polyvinyl Chloride (or Trade Name) Contains Vinyl Chloride Vinyl Chloride is a Cancer-Suspect Agent *Regulated areas means any area where vinyl chloride concentrations may be in excess of the permissable exposure limit. **Emergency means any occurrence such as, but not limited to, equipment failure or operation of a relief device which is likely to or does result in massive release of vinyl chloride. A-40 BOR 012146 8.2 Labeling and Identification (continued) 8.2.3 OSHA Labeling Requirements (continued) 8.2.3.6 Vinyl chloride shall be leqibly labeled either Vinyl Chloride Extremely Flammable Gas Under Pressure Cancer-Suspect Agent or in accordance with 49 CFR Parts 170-189 with the additional legend- applied near the label or placard Cancer-Suspect Agent 8.2.3.7 No statement shall appear on or near any required sign, label or instructions which contradicts or detracts from the effect of any required warning, informations or instruc tions . All transportation equipment (tank trucks, tank cars, barges or ships) not subject to labels as specified above shall be labeled in accordance with the requirements set forth in applicable Department of Transportation and United States Coast Guard regulations. Department of Transportation Requirements - Each container of vinyl chloride including tank cars shall cai^y an identifying label. The proper shipping name, Vinyl Chloride, as shown in the commodity list (172.101) must be used and shown on the outside shipping container per paragraph 172.300. Unless excepted each individual container must bear the FLAMMABLE GAS label as described in paragraph 172-417. Department of Transportation 172.328 requires that tank motor vehicles transporting vinyl chloride shall be marked on both sides and at the front and rear with letters at least four inchc high with words "Vinyl Chloride". The words "Flammable Gas" mus be displayed on other motor vehicles transporting 1,000 pounds or more gross weight per paragraph 177.823 (a). Each railroad car must bear the "Flammable Gas" placard per paragraph 177.823 (a). Paragraph 173.29 (f) specifies that an "Empty" label must be applied to containers which have been emptied and on which the old label has not been removed, obliterated or destroyed. It must be so placed on the container to completely cover the old label. r* O A-41 bor 012147 8.2 Labeling and Identification (continued) 8.2.3 OSHA Labeling Requirements (continued) 8.2.3.7 Paragraph 172.510 (c) specifics that a "Flammable Gas-Empty" placard shall replace or cover the "Flammable Gas" placard on the railroad tank car which has been emptied. The labels used should also conform with all other Federal, State and Local regulations relating to vinyl chloride such as the Federal Insecticide, Fungicide and Rodenticide Act; The Federal Hazardous Substances Act; The Federal Food, Drug and Cosmetic Act and other similar state and local legislations. 8.2.3.8 The Manufacturing Chemists Association also provides cards (Chem-Cards) containing information concerning the material as well as suggestions for safety precautions and emergency pro cedures. A copy of such a card is shown. These are of particu lar value accompanying bulk shipments. A-42 BOR 012148 MCA CHEM-CARD--Transportation Emergency Guide I CC-46 I February 1S76 Vinyl Chloride Compressed, liquefied gas; sweet odor. Gas is heavierthanair. HAZARDS (CANCER SUSPECT AGENT) | Extremely flammable. May be ignited by beat, sparks or FIRE open flame. Burning releases hydrogen chloride gas which is I i extremely irritating and corrosive. Fire may cause violent I rupture of tank. We- ---- -- -- -- -- --------------------- -- ----------- -- ------------ ----------- CVDACIIDC Vapor harmful. Liquid may cause skin or eye injury EXPOSURE sjn)i/of tQ fr05tbite' INC,'J V IF THIS HAPPENS For assistance, phone toil free, day or night DO THIS SPILL or LEAK Shut off ignition. No smoking or flares. Keep people away. Keep upwind. Shut off leak if without risk. Wear self-contained breathing apparatus and full protective clothing. Flush area with water spray. Run-off to sewer may create explosion hazard; notify authorities. Do not put out tire until leak haa been abut off. On small lire use dry. chemical or CO.. On large lire use water spray. Wear self-contained breathing apparatus Tanks in massive tlame contact may rupturo violently unless cooled by straight streams Ot water. Use unmanned monitor nozzle. Apply from side. Keep clear ol tank ends Other wise, withdraw from area and let lire burn. EXPOSURE Remove to fresh air. If unconscious, call a physician. If not breathing, apply artificial respiration, oxygen, in case of contact with liquid, thaw frosted parts with water. In case of exposure to gas from fire, administer oxygen if breathing is difficult. P*Oltthetf 6y iftt Mjrttfficturtnf auociJuoa inc itft tht CoffWtued &* fdltiblr Iho AtittuiiOhi nn airj.tir t*< mortftgftrt* ty ia am citai, rti'ftl ot <0 AUOt.4l.oft, n< . J|/*, In Ul A#f , N W , W*ih.ft|tQft 0. C. 70009. I*fi. ****** A U> A-43 BOR 012149 8.3 Non-Bulk Containers 8.3.1 General In many of the specific steps involved in the handling, loading, sampling and process of vinyl chloride, there are points of potential employee exposure to vinyl chloride monomer. Each facility working with vinyl chloride should identify what potential exposure points nay exist and perhaps be peculiar to their individual plant operations. When nec essary, engineering, work practice and personel protective controls must be provided as outlined by the OSHA vinyl chloride standard to control employee exposures to, at or below the permissable exposure limit. j 8.3.2 Cylinders 8.3.2.1 Cylinders should not be filled except with or by the consent of the owner and then only in strict accordance with the applicable Department of Transportation and OSHA renulations. 8.3.2.2 Areas where cylinders are connected or stored should have sufficient ventilation to prevent vinyl chloride concen trations from exceeding the OSHA permissable exposure limit. 8.3.2.3 Valve protection caps must always be kept securely in place except when the vinyl chloride containers are connected to piping, apparatus or equipment. As soon as the cylinder is disconnected the protective cap must be replaced. Empty vinyl chloride cylinders must be securely closed and capped. Air must not be allowed to enter the vessel. 8.3.2.4 Full or partly emptied cylinders should not be returned without permission of the supplier. Such cylinders must be shipped as full vinyl chloride cylinders and correspondingly., handled, labeled and tagged. 8.3.2.5 In shipping vinyl chloride cylinders, the bill of lading should give cylinder identification number. For each cylinder shipped, show the name of the cosignee and indicate whether the cylinder is empty or full. 8.3.2.6 Department of Transportation approved cylinders con taining vinyl chloride shall be legibly labeled in accordance with the requirements of OSHA and the Department of Transporta tion. (See Section 8.2) 8.3.2.7 Magnets or slings should never be used to unload cylin ders. When transporting by crane or derrick a suitable platform, cradle or boot should be used. 8.3.2.8 Care should be exercised not to drop cylinders or otherwise handle them roughly. A-44 BOR 012150 8.3 Non-Bulk Containers (continued) 8.3.2.9 Cylinders may be moved by tilting and rolling them on their bottom edge. Dragging and sliding them should be avoided. 8.3.2.10 When cylinders are.transported by hand truck, they should be held securely in position by means of a locking clamp, chain or other suitable holding device. 8.3.2.11 Cylinders should never be used as rollers for moving any object or material. 8.3.2.12 Avoid disturbing the fusible plug. The safety device should be tagged in order to differentiate it from the discharge connection. 8.3.2.13 Check valves must be installed in feed lines from the cylinder to prevent the reactants from entering the cylinder. 8.3.2.14 Cylinders should be provided with pressure regulators as recommended by the supplier. 8.3.3 Sample (Bomb) Cylinders Where applicable, the recommendations set forth for cylinders in the preceding, section also apply to sample bombs. 8.3.3.1 Stainless steel sample pressure bombs meeting the requirements of Department of Transportation regulation 3B-400 should be used to take quality control vinyl chloride monomer samples. Samples must be taken in bombs that are dedicated to vinyl chloride service. A closed loop sampling system which is designed to include the sample container is preferred in order to minimize the venting of vinyl chloride to the atmos phere . 8.3.3.2 Person(s) directly involved in the collection or analysis of vinyl chloride samples for quality control pur poses should wear NIOSH/MESA approved respiratory protection consistent with the requirements of the OSHA vinyl chloride standard. The type of respiratory device utilized should re flect actual or reasonably anticipated vinyl chloride exposure levels. 8.3.3.3 All quality control testing and analyzing should be performed in a laboratory equipped with a chemical laboratory hood having a capture velocity adequate to collect vinyl chloride vapors under conditions prevailing in the laboratory. The dis charge from the laboratory hood and from the analytical test instruments shall be designed so that vinyl chloride vapors do no re-enter a nonregulated area. 8.3.3.4 All quality control sampling containers (bombs) should be routinely inspected to assure the integrity of the valves a^^ for leakage. A-45 ' BOR 012151 8.4 Bulk Transport 8.4.1 General In many handling and unloading steps there are potential points of exposure to vinyl chloride monomer. Consult with the technical service staff of the supplier regarding where monomer unloading exposure points may be in your plant. Check also for other exposure points that are peculiar to individual plant operations. Design of bulk transport facilities varies and unloading procedures are usually specified by the supplier. Com plete understanding between the supplier and the user with regard to equipment and procedures is essential to safety of the transfer operation. Loading or unloading bulk containers should be considered a hazardous operation and OSHA regulations regarding signs, barricades and respirator use followed. 1. EPA does not approve control devices. The control device used must meet the emission levels. 2. Allow no vehicular traffic in the area during transfer. If this cannot be done, min*"ize and control traffic by temporary road blocks. 3. If a sample is required before transfer for testing purposes, a stainless steel sample bomb meeting the Department of Transportation's re quirements and dedicated to vinyl chloride service should be used. A closed loop sampling system is preferred. The operator taking the sample must use a suitable respirator and appropriate personnel protective equipment during the period of sampling. Bulk containers delivered with defective valves or other equipment should be held pending instructions from the owner. Only such actions should be taken that will provide for con trol of immediate safety problems such as obvious leaks and spills. A-46 BOR 012152 8.4 Bulk Transport (continued) 8.4.1 General (continued) In these cases remove sources of ignition. Keep people away. Control the leak by plugs, valves or patches to the extent that the immediate hazard is controlled. Personnel potentially exposed to vinyl chloride vapor should wear NIOSH/MESA approved air supplied respirators. 8.4.2 Miscellaneous Items Where access to the top of the tank car or truck is needed, the spot should be provided with stairs and a platform of non combustible construction. Overhead piping and equipment should be counterbalanced for ease of handling. An emergency shower and eye bath should be directly accessible and within twenty-five feet of the loading or unloading spot. Fittings - The packing and lubricant for valves and piping must be of a material recommended for vinyl chloride handling. Pumps and compressors must be equipped with double mechanical seals on packing glands. Space between the seals must bo vented to an EPA-approved control device or purged with a pressurized fluid so that there is no external leakage of vinyl chloride. Unloading or loading piping should be provided with excess flow check valves to control spills in the event of a line break. All unloading or loading piping must be attach'd to an EPA- ^ approved control system to limit atmosphere emissions to 0.13 FTJ at STP for each disconnect. The use of slip gauges is forbidden unless EPA-approved control devices are provided to control the emissions. 8.4.3 Tank Trucks 8.4.3.1 Tank trucks should be visually inspected for leaks and to confirm the contents before they are allowed to enter the plant. Unloading or loading should be performed only during daylight unless the working areas are adequately lighted. 8.4.3.2 The tank truck pad should provide two feet clearance on each side of the truck and four feet at each end. The pad should be sloped to drain spills away from the truck and exposed struc tures, Tank truck wheels should be blocked and brakes set to prevent movement during loading or unloading and the engine stopped. If the tractor must be separated from the trailer, this must be done before making any connections and place an adequate brace under the front end. A-47 BOR 012153 8.4 Bulk Transport (continued) 8.4.3.3 Static electricity is often generated by the tank truck in transit or it may be generated by the loading or unloading operation. All pipinq, tanks and structures should be electrically bonded by conductors that are adequate for power or lightning protection before any work is initiated. (See NFPA #77). 8.4.3.4 All sampling must be done with EPA-approved systems to minimize vinyl chloride emissions to the atmosphere. 8.4.3.5 Unloading or loading operations should conform to the owner or operators instructions. On completion of the oper ation, loading or unloading hoses must be evacuated as noted previously and wheel blocks removed. 8.4.3.6 The truck engine should be started and the true1 removed only after all connections are severed and the absence of flammable gases confirmed by test. 8.4.4 Tank Cars Tank cars are the most commonly used bulk container for vinyl chloride shipment. All are unloaded from the top .nrough one or both of the liquid eductor tubes. A third valve provides access to the vapor space of the car for purposes of padding or pressurizing the car to prime the unloading pump. Sampling slip gauging and unloading hose emissions are subject to the same EPA limitations noted for tank trucks. 8.4.4.1 Shippers and/or owners instructions should always be followed and all caution markings on both sides of the tank and dome should be read and observed. If inspection shows the car has faulty equipment or is leaking, the shipper should be contacted for instructions. Shippers' plants and procedures vary; thus, instructions should be obtained regarding loading or unloading a vinyl chloride tank car. 8.4.4.2 The car unloading track should be level and the engine crew should accurately spot the car at the unloading lines. 8.4.4.3 The tank car brakes must be set and the.wheels blocked prior to hookup of the pipelines. Unless the car is protected by a closed locked switch,, derails should be placed approximately one car length from each end of the car. 8.4.4.4 Caution signs and warning lights prescribed by Depart ment of Transportation regulations must be placed at the derails on the track to warn persons or trains approaching the car from open end or ends of the siding. These must remain in place until the car is ready to be moved. A-48 BOR 012154 8.4 Bulk Transport (continued) 8.4.4.5 The contents of the car should be verified by checking the car number with the shipping papers. Many companies also sample the contents for analysis. Failure to verify the car contents can lead to serious and hazardous mixing of reactive chemicals. 8.4.4.6 Typical Unloading Situation Tank cars of vinyl chloride are filled with liquid up to no more than 86% of the water weight capacity of the tank. Vinyl chloride vapor occupies the space above the liquid. Air or oxygen must not be introduced during unloading or storage to prevent formation of a flammable mixture or premature polymeri zation. Purge all lines thoroughly with nitrogen before hooking up. Use nitrogen with a masimum of ten ppm oxygen. Nitrogen purging can be minimized by sealing the line and alternately pressurizing with nitrogen and bleeding off the nitrogen to a remote recovery system or incinerator. Remove the threaded pipe plugs on the liquid and gas valves cautiously and connect the liquid unloading line and the vapor padding line. The vapor pressure is needed to prime the centri fugal forwarding pump, if one is used. To reduce pressure drop, locate the pump as close to the tank car as possible. Some in stallations have a compressor on the vapor line from the storage tank in addition to the pump. In warm climates, a compressor may be used alone without a pump, but in cold weather a pump ifflk usually needed - with or without the compressor - to facilitata^F unloading. The vapor pressure used for padding should not exceed 225 psig. Never apply heat to accelerate the unloading of a vinyl chloride tank car. To obtain flexibility in the' unloading system, either stainless steel hose or steel pipe with flexible joints can be used. The flows of vinyl chloride from the tank car should be regulated by a valve in the transfer line. If the discharge rate suddenly becomes too great, an excess flow check valve in the tank car will close. To re-open this valve, close the unloading connection valve until the pressure is equalized. Start unloading by slowly opening the vapor padding connection valve to the car. If it is necessary to discontinue unloading for any reason, close all valves tightly and disconnect all un loading connections. The lines leading from the unloading connection valve and the padding connection valve should be purged with nitrogen so that the vinyl chloride monomer vapor in those lines is transferred to the recovery system. A-49 bob. 0123-55 8.4 Bulk Transport (continued) 8.4.4.6 Check the storage tank frequently to determine when the tank car is almost empty. Completely unload the tank car; it should not be used for storage. A pressure gauge on the unloading line is the best way to indi cate when all the liquid has been emptied from the car. After the car is emptied, stop the transfer pump. Close the padding connection valve and then the unloading connection valve at the top of the car. After this, close all other valves in the vinyl chloride line. The lines leading from the unloading connection valve and the padding connection valve should be purged so the vinyl chloride monomer vapor in those lines is transferred to the recovery system. Check the vinyl chloride monomer concentration to make sure there are no invisible leaks from valves. Wear respiratory protection if there is any leakage. Take care of leaks as recommended. Do not 'llow tank car to stand with unloading connections attached after unloading has been completed. Remove all lines from the car and disconnect grounding wires. Reverse the "Flammable Gas" placard on the car so that it reads "Flammable Gal-Empty". IMPORTANT __ Leave at least 5-10 psig of vinyl chloride vapor pressure in the empty tank car being returned after closing and sealing all openings. The pressure is necessary to prevent, air from entering the car. 8.5 Shipping 8.5.1 Department of Transportation Classification and Regulations Vinyl chloride is classified by the United States Department of Transportation as a flammable gas. When shipped by rail, water or highway it must be packaged in authorized containers and shippers must comply with Department of Transportation regula tions regarding packaging, loading, handling, labeling, marking and placarding. (R. M. Graziano's Tariff No. 31, 1977 is a source of condensed Department of Transportation Regulations for Hazardous Materials.) A-50 BOR 012156 8.5 Shipping (continued) 8.5.2 Shipping Containers - Type and Size Title 49 CFR Transportation Part 173.304 Cylinders - 4B15Q, 4BA225, 4BW225, 3A150, 3AA150, DOT-25 and 3E-1800. Cylinders with brazed seams are not permitted. Maximum filling density - 84%. Title 49 CFR Transportation Part 173.315 Requirements for Compressed Gases in Cargo Tanks MC-330 and 331. Maximum filling density - 84%. Title 49 CFR Transportation Part 173.314 Requirements for Compressed Gases in Tank Cars DOT 106A500X Maximum filling density - 84%. DOT 105-200W Maximum filling density - 87%. DOT 112A340W Maximum filling density - 86%. DOT 114A340W Maximum filling density - 86%. 8.6 Transportation Emergencies 8.6.1 Assistance Available 8.6.1.1 CHEMTREC (CHEMical Transportation Emergency Center) This center, located in Washington, D. C. at the offices of the Manufacturing Chemists Association, is manned 24 hours per day, seven days a week, and provides by telephone immediate response/action information for police, fire fighters and others concerned with the control of chemical transportation emergency situations. A-51 BOR 012157 8.6 Transportation Emergencies (continued) 8.6.1 Assistance Available (continued) 8.6.1.1 CHEMTREC (continued) For assistance, dial: *(800) 424-9300 in the 48 contiguous States of the USA. *(800) 483-7616 in District of Columbia. *(200) 483-7616 in Alaska. In Canada, call Canadian Chemical Producers Asso ciation's TEAP (Transportation Emergency Assistance Plan). *Use long distance prefix if needed. 8.6.1.2 Company Mutual Aid A number of vinyl chloride manufacturing companies voluntarily participate in a mutual-aid organization under which, in the event of a transportation accident, the closest company vinyl chloride plant will dispatch a qualified adviser to the scene of the accident if requested to do so by the shipper of the commodity. 8.6.2 Emergency Control 8.6.2.1 Personnel Attending Accident Scene Shippers' representatives do not take charge of emer gency operations. They are present as advisers only. 8.6.2.2 Recommended Emergency Kit The following are considered essential: a. Explosion meter b. NIOSH/MESA approved self-contained breathing apparatus c. Wood plugs and wood mallet d. Data sheet and pencil e. Camera and film f. Flashlight (Bureau of Mines approved) g. Rubber gloves h. Slicker suit i. Rubber overshoes j. Safety lines (braided stainless, plastic covered) and harness A-52 BOR 012158 f 8.6 Transportation Emergencies (continued) 8.6.2 Emergency Control (continued) 8.6.2.2 Recommended Emergency Kit (continued) k. Goggles l. Safety hat m. 0-rings n. Strap wrench o. Ten-inch adjustable wrench p. Screwdriver q. Ground continuity meter r. Large first aid kit and collapsible water container, approximately fifty gallons. The water container should be filled at the emer gency site and be available for eye wash or treatment of chemical skin contacts. 8.6.2.3 Recommended Procedures Leaks of Vinyl Chloride I. Controllable Leaks a. Small holes: Drive wooden plugs. b. Larger holes: Neoprene patch, bonded or chained to tank. Special rigs should be left to the judgment of the man at the scene. c. Jagged holes are difficult t . close. d. potassium bicarbonate will extinguish a vinyl chloride fire but reignition often occurs. Os/2 it around valves if it appears that a leak can be subsequently controlled. II. Uncontrollable Leaks - No Fire a. Evacuate area and isolate. b. Remove sources of ignition. c. Control spread of vapors by water spray. III. Uncontrollable Leaks - Fire a. Evacuate and isolate area. b. Keep adjacent cars cool, if possible, with water spray. c. Keep nonessential personnel away. d. Treat a non-burning tank car in vicinity of fire as if it is about to rupture. e. If vinyl chloride gets to a sewer, evacuate area and flush sewers with fire hoses. I A-53 BOR 012159 8.6 Transportation Emergencies (continued) 8.6.2 Emergency Control (continued) 8.6.2.4 Spilled Vinyl Chloride Spilled vinyl chloride should not bo deliberately ignited. 8.6.2.5 Recovery or Removal of Vinyl Chloride Depending upon circumstances and extent of car damage, vinyl chloride may be recoverable, but recovery should not be the determining factor in controlling the situation. a. If car condition permits, transpfer contents to empty tank car using nitrogen pressure. b. If car is ruptured, attempt to use pump wit"', flooded suction. c. If pumping is impractical, use water or oil to float out remainder of vinyl chloride. d. Fill empty tank with water or nitrogen e. If a vinyl-ice mixture forms, keep a water stream on the tank until it dissipates. f. Handling of vinyl chloride in a damaged car can be influenced by weather conditions. At low temperatures, since vaporization is reduced, patch tank, if possible, so that it can be moved. 8.6.3 Marine Emergencies 8.6.3.1 United States Coast Guard regulations (refer ence Vinyl Chloride Coast Guard Standard, i.e. Parts 40, 151, and Chapter 1 of Title 46 CFR. . .) require that a cargo information card for vinyl chloride be carried aboard the tank barge mounted near a warning sign anr. in such a position as to be easily read by a man stand ing on the deck of the barge. The cargo information card shall also be carried on the bridge or in the pilot house of the towing vessel. Copies are available from the Manufacturing Chemists Association. 8.6.3.2 Special Safety Equipment In addition to normal safety equipment provided at the dock, the following special items should be available: a. NIOSH/MESA approved self-contained breathing equip ment (at least two and two spare bottles). b. Explosimeters. c. Ground continuity meter. A-54 BOR 012160 8.6 Transportation Emergencies (continued) 8.6.3 Marine Emergencies (continued) 8.6.3.2 Special Safety Equipment (continued) d. Water with an appropriate number of nozzles. e. Dry chemical fire extinguisher. f. MCA Chemical Safety Data Sheet SD-56 and Cargo Information Card CIC-80. 8.6.3.3 Recommended Emergency Procedures 8.6.3.3.1 Leaks of Vinyl Chloride ' I. General - Activate Alarm II. Controllable Leaks - No Fires a. Evacuate area of nonessential personnel and isolate leak from source. b. Eliminate ignition source. c. Control spread of vapors by water fog. d. Attempt to repair leak using adequate safety protection procedures. III. Uncontrollable Leaks or Rutpures - No Fires a. Evacuate area of nonessential personnel and isolate area. b. Remove all sources of ignition. c. Use water spray to prevent accumulation of liquid and to dissipate vapor cloud. It is not recommended that the ship's fi:;e water supply be hooked into the city water supply. IV. Uncontrollable Leaks - Fire a. Isolate area. b. Evacuate area except for emergency personnel. c. Use water fog on fires and fumes (do not extinguish fire unless leak can be controlled) d. Use copious amounts of water to keep adjacent areas cool. e. Treat adjacent tanks as if about to rupture. f. Make provisions to minimize the mixing of air with vinyl chloride vapor in confined spaces and the burning tanks or line (water, Nj or inert gases). 8.6.3.3.2 Spilled Vinyl Chloride Spilled vinyl chloride should not be deliberately ignited. A-55 BOR 012161 Transportation Emergencies (continued) 8.6.3.3 Recommended Emergency Procedures (continued) 8.6.3.3.3 Recovery or Removal of Vinyl Chloride Depending upon circumstances and the extent of the tank damage vinyl chloride may be recoverable but provisions must be made to keep air out of the tank. a. If tank condition permits, transfer contents to an empty tank or back to shore. b. If tank, cannot be patched and it does not have a deep well pump or the deep well pump cannot be used, sparge heated nitrogen into the bottom of the tank to vaporize the vinyl chloride. BOR 012162