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*^ INDUSTRIES PPG INDUSTRIES, INC. CHEMICAL DIVISION - U.S. P. 0. BOX 1000 LAKE CHARLES, LA. 70602 December 6, 1985 Hr. John T. Barr Air Products and Chemicals Corporate Environmental P. 0. Box 538 Allentown, PA 18105 Dear John, I circulated the VCM storage guidelines and got a few comments and typo corrections. A copy is attached. Do you have a copy of PPG's VCM Manual? If not, Roy Stack in Pittsburgh, telephone (412)434-2403, can send you one. I sent some comments to Mark Tawney of BFG a few years ago after they made the presentati n at VCSA on the spill from the sphere. A copy of my letter is attached. If you have any questions on this, please give me a call at (318)491-4810. BDR/hl attachment File BARRLTRBDR SL 089316 V r S PvV. - ^ PPG INDUSTRIES, INC. CHEMICAL DIVISION - U.S. P. 0. BOX 1000 LAKE CHARLES, LA. 70602 January 10, 1983 Mr. Mark D. Tawney The B. F. Goodrich Company Chemical Group 6100 Oak Tree Boulevard Cleveland, OH 44131 Dear Mr. Tawney: I appreciate you sending me a copy of your "Vinyl Chloride Storage Tank Safety Standard". I have forwarded a copy to our Superintendent Prevention and Industrial Engineering. At the present time PPG d have a written standard for VCM storage vessels, except for some written in 1978 for storage of large quantities of refrigerated f These guidelines were developed prior to design and construction > temperature VCM storage facility which was started up in 1981. We harm,"* however, addressed most of the items in your safety standard either as a result of insurance or code requirements, or as indicated by past experience. Some other safety/reliability items worth considering are: 1. No threaded connections should be attached to the tank. 2. Each vessel opening should be a minimum of l*s" pipe size and have a flanged valve attached directly to the vessel. 3. Thermowells should be welded on to flanges, i.e. no wells simply screwed into drilled and tapped flanges or screwed into threaded couplings on the vessel. 4. The only three-way, two-port, full-bore, transflow valve we have approved for installation beneath relief valves is a KTM Model //E03162L/FS-32GJ-15-S. The other valves we have looked at either had reduced port openings or could isolate the vessel from the relief valves in certain positions. 5. We bench test safety relief valves on storage vessels every two years. 6. We feel proof-testing of critical instrumentation on storage vessels is very important. Critical alarms (high level, high pressure, etc.) are tested every 6 months. Vapor detectors are tested and calibrated every 3-4 months. SL 089317 r ' Tavney, Mark D. Page 2 7. We experienced a lot of problems with the Continental rupture discs beneath the SRV's on our low-temperature VCM tanks. They supplied high pressure vacuum supports with the low pressure discs. The membrane would rupture at the correct pressure, but the vacuum support would not go, even at twice the rated pressure. We feel confident this problem has been resolved for us, but it would be worth checking if you have any Continental discs in the 2-15 psig range. You may be interested in some British publications which pertain to storage of VCM or other flammable liquids. 1. "Guides to Safe Practice for Chemicals - Precautions Against Fire and Explosion - Vinyl Chloride", The Chemical Industry Safety and Health Council of the Chemical Industries Assoc. Ltd., Alembic House, 93 Albert Embankment, London, SE1 7TU. (1978) 2. "Guide for the Storage and Use of Highly Flammable Liquids", Chemical Industry Safety and Health Council of the Chemical Industries Assoc. Ltd - (address same as above). (November, 1977) | If you have any further questions or comments please feel free to call me^ (A.C. 318-491-3ft) Wio ; SL 089318 F 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 local 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. C&ST 1^ 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. f,itzuu~r (A 5Pro- 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 ri commended 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 SL 089319 8.1 Storage (continued) 8.1.2 Conditions of Storage (continued) leakproof integrity. Wherever po:.v. i b 1 <, all ,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 " ments. Vinyl chloride tanks should be pai white or other heat reflective paint. (C) All storage areas should have install' 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 b pro vided in all storage areas to completely confine ancl 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 storage 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 SI, 089320 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, regulating areas to authorized individuals, environmental monitoring, respiratory pro tection, laheling, 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 whe ' vinyl chloride is wet even at ordinary temperatures. This may be due to the presence of impurities. In contact with 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 the 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 containinq 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 Si 8932l 8.2 Labeling and Identification (continued) 49 CFR 172-417 - Small cylinders should have ? four-inch "Flammable Gas" label which is red in color and has black printing and cylinder marked with "Vinyl Chloride". 5172.417 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 be red in color with wh:te lettering. A-37 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 .... 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 S1 S9323 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 desiqned 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 lab 1# 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. CHLORIDE DANGER! EXTREMELY FLAMMABLE LIQUID AND GAS UNDER PRESSURE HARMFUL JF JNHALED MAY POLYMERIZE VIOLENTLY UNDER FIRE CONDITIONS OR LOSS OR REMOVAL OF INHIBITOR Keep a way from heat, sparks, and open flame. Keep container closed. Use with adequate ventilation. Avoid breathing vopor. Avoid contact with skin. Keep cyl imlcr out of sun and away fiom lu'at. Container should bo gioundcd when being emptied. Never drop cylinder. FIRST AID; If inhaled, rmnovc to fresh air. If not breathing give artificial respiration, preferably mouth-to-moulh. If breathing is difficult, give oxygen Call a physician. In case of: A-39 SL 089324 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 permissablc exposure limit. **Emergency means any occurrence such as, but not limited to, equipmen failure or operation of a relief device which is likely to or does result in massive release of vinyl chloride. A-40 SL 089325 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 Presvure 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 Requiremerits - Each container of vinyl chloride including tank cars shall cai*"/ 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 inches high with words "Vinyl Chloride". The words "Flammable Gas" must 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. A-41 SL 08932s 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 SL 089327 MCA CHEM-CARD--Transportation Emergency Guide |--CC-46 j February 19761 l ,, I Vinyl Chloride Compressed, liquefied gas; sweet odor. Gas is heavierthanair. HAZARDS r J FIRE i (CANCER SUSPECT AGENT) W. --------- ----------------------------------------- --------- - -- * -- ------------------- Extremely flammable. May be ignited by heat, sparks or open flame. Burning releases hydrogen chloride gas which is 1 extremely irritating and corrosive. Fire may cause violent rupture of tank. EXPOSURE i ^ _ __ _ Vapor harmful. Liquid may cause skin or eye injury similar to frostbite. IF THIS HAPPENS For assistance, phone CHEMTREC toll 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. So not put out lire until leak has been shut off. On small lire use dry chemical or CO.. On large lire use water spray. Wear self-contained breathing apparatus. Tanks in massivo name contact may rupture violently unless cooled by straight streams Ot water. Use unmanned monitor nozzle. Apply Irom side Keep clear ot lank ends Other wise. withdraw from area and tat tire bum. 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. PuOiriMd of t% uanu'Ktuf'1-1 C'ifw.tu Ai\ocit<on uk riii(p* I A* Alifti '***# hi aifJitlr ibal tr> W>nulKtwiiA| trem,ill Anoi,. align in. tnwrttia* mats tfu Comei*ut Aiw-ittw .mormilidn n m an tHM COtrtC! Of iultinffll , Hit, W#h n|to* 0. C, 2000* l*'.' **** . U5* A-43 SL 39328 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 may 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 reaulations. 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 SL 089329 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 slidinq 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 r fleet 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 he designed so that vinyl chloride vapors do norre-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 and for leakage. A-45 ' SL 0M330 8.4 Bulk Transport 8,4*i General ^}an<^in9 and unloading steps there are potential wi(. f,_of exPfure to vinyl chloride monomer. Consult tec^nicai service staff of the suppoar regarding , mnomer unloading exposure points may be in your Check also for other exposure roints that are peculiar to individual plant operations. ^ulk transport facilities varies and unloading olete unrff af6 "sually specified by the supplier. Comreaarri *- erstfn<*in9 between the supplier and the user with of fho 1.0 ^uipment 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. i 1. _ EPA does not approve control devices,- ^he If control device used must meet the emission levels. -------- w VM*WH*ai 411 transfer, if this cannot be done, min^nize and control traffic by temporary road blocks. * f a sample is required before transfer for fn9 purposes, a stainless steel sample bomb meeting the Department of Transportation's re- eh^rf!?ewtS and dedicated to vinyl chloride service Jd used. A closed loop sampling system is [j erreY* The operator taking the sample must / n a suitable respirator and appropriate personSe* P ective 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 and spills. safety problems such as obvious leaks A-46 SL 089331 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. i Pumps and compressors must be equipped with double mechanical fOr*seals on packing glands. Space between the seals must bo vented ' toan EPA-approved control device or purged with a pressurized _----" Tluid so that there is no external leakage of vinyl chloride. S'ee p/oV 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 attacr. ~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 SL 089332 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 piping, tanks and structures should be electrically bonded by conductors that arc 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 trueremoved only after all connections are severed and the a'^s-tnee 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 .trough one or both of the liquid eductor tubes. A third valve provid s 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 SL 089333 8.4 Bulk Transport (continued) 8.4.4.5 The contents of the car should be verified by checkinq 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 maVimum of ten ppm oxygen. Nitrogen purging can be minimized bysealing the line and alternatjly 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 is usually needed - with or without the compressor - to facilitate 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. art 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 leadinq 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. ei\sor<L \ w A"49 Wa ((\ -U t-O /\Whr SL 089334 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 ttose 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. ft ft "V* ^ Reverse the "Flammable Gas" placard on the car so that it reads "Flammable G^-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 SL 089335 8-5 Shipping (continued) 8.5.2 Shipping Containers - Type and Size Title 49 CFR Transportation Part 171.304 Cylinders - 4B150, 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 SL 089336 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 8.6 Transportation Emergenci s (continued) 8.6.2 Emergency Control (continued) 8.6.2.2 Recommended Emergency Kit (continued) 8.6.2.3 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. A ydJ- 44^.# VC ^v, 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. Us,e it around valves if it appears that a leak can be subsequently controlled. XI. 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. A-53 SL 089338 8.6 Transportation Emergencies (continued) 8.6,2 Emergency Control (continued) 8.6.2.4 Spilled Vinyl Chloride t Spilled vinyl chloride should not be deliberately ignited. j 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, transfer 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 and 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 SL 089339 8.6 Transportation Emergencies (continued) 8.6.3 Marine Emergencies (continued) 8.6.3.2 Special Safety H|U ipmont (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 personn 1 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 089340 Sh 8.6 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. A-56 Si esj4l