Document 3BnG4pwmqBgYwOqb8EnveLb0

handling and properties Contents PPG's commitment to vinyl chloride monomer production Properties Hazards Work practice guidelines Handling and unloading Tank cars Tank trucks Storage tanks Methods of analysis Purchasing information Percarbonate initiators 4 7 11 14 18 19 25 30 34 35 36 ucc 059481 Copyright 1975. PPG Industries. Inc. 9> Commitment PPG's Commitment To Vinyl Chloride Monomer Production In 1969. PPG expanded its Lake Charles. Louisiana vinyl chloride plant and. in 1971, built a Puerto Rican plant that greatly expanded PPG's capacity for producing chlorine and vinyl chloride monomer. Built at the same time nearby in Puerto Rico was an olefins plant half-owned by PPG. Its annual capacity includes one billion pounds of ethylene, which PPG com bines with chlorine to produce vinyl chloride monomer. A new large tanker, the S.S. Puerto Rican, transports refrigerated vinyl chloride monomer to a terminal at Paulsboro, New Jersey. There vinyl chloride monomer is stored under refrigeration and shipped to customers in tank cars and in a fleet of dedicated tank trucks. PPG can also ship vinyl chloride monomer at ambient tempera tures by barge and ocean-going ships as well as by pipeline. PPG produces vinyl chloride monomer by an oxyhydrochlorination process and holds more than 400 domestic and foreign patents on this technology. PPG developed the process in the early 1950s and commercialized it in the early 1960s. Related to PPG's vinyl chloride monomer is its production of vinylidene chloride monomer. ucc 059482 4 .inTnaaiUtFa t-1 ti~* PPG p!ar_: r Guayanilla. Puerto Rico, t-e company's mocerr 3-t.OOO-ton chemical tinker. S.S. Pue'tc Hicar.. receives a load of v.oy, erlorde montmer mat will travel under refrigersticn to rat store. New Jersey. In the foreground i$ the refrigeration unit of a vinyl chloride monomer storage tank at the Pauisooro. New Jersey terminal. This is the nation's largest terminal for vinyl chloride monomer and the world's largest for refriger* ated vinyl chloride monomer. "5"*; :r,c< >s oe *r 'catted with 20 tons of p . ., c*i;- oa - c-:n-er under pressure. PPG offers the East Coast's f rst tar< truck deliveries of vinyl chloride monomer. Tne Paulsboro terminal can stdre 53.3 million pounds of the monomer. ucc 059483 5 At PPG'$ Lake Charles. Louisiana plant, a tank car is being loaded with liquid vinyl chloride monomer under pressure. PPG has a fleet of tank cars dedicated to vinyl chloride sen/ice. Norwegian vessel has taken on a cargo tank of liquid vinyl chlonde monomer under pres sure from the PPG plant in Lake Charles, Louisiana. PPG loads ships with up to six million pounds of monomer. Barge holding cargo tanks of liquid vinyl cnloride monomer under pressure is being loaded at the PPG plant in Lake Charles. Louisiana. From there, the barge can travel up the Mississippi ana Ohio rivers. A barge can hold up to four million pounds of monomer. Storage spheres at PPG's Lake Charles, Louisiana plant hold thousands of gallons each of liquid vinyl chloride monomer under pressure. Horizontal storage tanks at right serve as quality control tanks. 6 ucc 059484 Properties Chemical Names: Vinyl chloride, vinyl chloride monomer, chloroethylene, chloroethene Chemical Formula: CHiCHCI Molecular Weight: 62.5 Description: At ordinary temperatures and pres sures, vinyl chloride is a colorless gas with a mild, sweet odor. But as sup plied in tank cars and trucks under pressure, it is a liquid. Vinyl chloride is highly volatile and its vapor is extremely flammable. Containers are labeled "cancer-suspect agent." Boiling Point. 8C 8F --13.8 +7.0 Freezing Point. 'C F --153.7 --245 Flash Point open cup. C 8F --78 --108.4 Explosive Limits, volume % in air at 258C (778F) 3.6 to 33 Autoignition Temperature. C 472 8F 882 Critical Temperature, C 8F 158.4 317 Critical Pressure, psia Vapor Density, air--1 Solubility. water in monomer at 258C (77 8F). weight % 775 2.15 0.11 8 Solubility Vinyl chloride is relatively insoluble in water but soluble in most organic solvents. Reactivity. Vinyl chloride polymerizes exother mically in the presence of light, air, oxygen or catalysts. Heat alone will not initiate polymerization. Vinyl chloride is thermally stable to quite high temperatures. Although peroxide formation due to air exposure is a slow reaction, certain peroxide products are shock-sensitive. Vinyl chloride is noncorrosive to metals when dry at normal ambient temperatures, but water at elevated temperatures accel erates corrosion. The double bond behaves as in other unsaturated com pounds. The chlorine atom is relatively inactive and is more stable than in saturated or allylic compounds. ucc 059486 i l " ' i -1 warn Specification and Typical Analysis: Appearance Color Acidity, as HCI, ppm Iron, as Fe. ppm (filtered sample) Nonvolatile residue. weight % Water, ppm Sulfur, as S0a, ppm Acetaldehyde, ppm Acetylene, ppm Specification clear, free of suspended matter colorless, water-white 5 maximum 0.5 maximum 0.05 maximum 100 maximum 3 maximum 5 maximum 2 maximum* Typical Analysis clear, free of suspended matter colorless, water-white <1 0.1 0.0003 34 <1 <1 <1 "Trs maximum is an industry standard: however, the PPG product contains nc datettable amount cf acetylene. UQUIO DENSITY TEMPERATURE. t**g* Ctrttfertd* PRESSURE, millimeters mercury VAPOR PRESSURE -20 -10 0 10 20 30 40 SO 60 70 80 90 100 TEMPERATURE, degrees Centigrade ucc 059488 Fire and expi sion Vinyl chloride vapor is extremely flammable. Its explosive limits are between 3.6 and 33% by volume in air. Sufficient ventilation and the elimination of ignition sources are mandatory in areas where vapor con centrations may reach a flammable level. When a tank car is unloaded, both the car tank and the unloading pump must be electrically grounded. The major products of combustion include toxic and corrosive hydrogen chloride as well as carbon monoxide and carbon dioxide. Under certain conditions traces of phosgene may be produced. The main sources of danger to personnel result from carbon monoxide and from the extensive formation of hydrogen chloride gas, as well as from any unburned vinyl chloride vapor. Since a major com bustion product is hydrogen chloride, any time its pungent odor is detected the area should be evacuated. Only persons properly protected should enter the area. Vinyl chloride vapor does not have any warning properties at low levels. Chemical reactions Carbon dioxide or dry chemical agents extinguish small fires effectively, but no extinguisher is known for large fires. Streams of water cannot extin guish a liquid vinyl chloride fire because the monomer does not mix with water and will float on top. Water may be sprayed to cool equipment, however. If the source of the vinyl chloride monomer leak has not been closed off. do not attempt to extinguish a large fire because hot metal can reignite an unburned vapor cloud. No one without proper protective respira tory equipment should enter an area where there has been a fire until the area has been thoroughly ventilated and checked to make sure the monomer concentration is below the level re quired by the Occupational Safety and Health Standard. Contamination of uninhibited vinyl chloride monomer may catalyze polymerization, which is highly exo thermic. or cause decomposition, which liberates toxic hydrogen chloride gas. The high purity of vinyl chloride must be maintained in shipment, transfer and storage. Exposure to oxygen, air or sunlight can also catalyze polymerization. Peroxides may also form. Toxicity The Occupational Safety and Health Standard on exposure to vinyl chloride published October 4. 1974, says: "Based on the demonstrated evidence of vinyl chloride monomer's carcino genicity in three animal species (rats, mice and hamsters), and the sub stantial probability that vinyl chloride monomer had been the causal agent in the cases of liver angiosarcoma found in workers both here and abroad, OSHA . .. published a comprehensive proposal... to protect employees from hazards of exposure to vinyl chloride monomer," I I I I I B I I B ucc 059490 I f 12 Stated in this OSHA standard is the following "Permissible exposure limit" scheduled to become effective April 1.1975: (1) No employee may be exposed to' vinyl chloride at concentrations greater than 1 ppm (part per million by volume) averaged over any 8-hour period, and (2) No employee may be exposed to vinyl chloride at concentrations greater than 5 ppm averaged over any period not exceeding 15 minutes. (3) No employee may be exposed to vinyl chloride by direct contact with liquid vinyl chloride. In cases where these limits of exposure are exceeded, the wearing of respira tors will be mandatory for workers beginning April 1,1976. Until then, the wearing of respirators is discre tionary for exposures under 25 ppm. Besides the suspected carcinogenicity, vinyl chloride monomer vapor can pro duce immediate symptoms in persons exposed to high concentrations. The odor of vinyl chloride monomer is sweetish and the sense cf smell can not be relied upon as a warning. High vapor concentrations may cause lung irritation, can cause dizziness and anesthesia, and may do ether bodily damage in ways not yet ascertained. In all cases of overexposure, immedi ately remove the affected individual to fresh air and obtain medical attention. Liquid vinyl chloride monomer may cause frostbite because it evaporates so fast. If a polymerization inhibitor is included, it may cause local skin burns. However, most vinyl chloride monomer shipped today is not inhibited. Workers should wear eye protection and protective clothing to prevent skin contact with the liquid. If vinyl chloride gets on clothing or shoes, they should be removed immediately. If vinyl chloride contacts toe skin, wash immediately with soap and water. If vinyl chloride contacts the eyes, the eyes should be v. asned immediately and thoroughly with water for at least 15 minutes. Get medical attention. Workers shoulc wear protect:.* doming and eye protection when unloading soiements. Whether or not respirarory pr;:eor o~. <s used and wha: type, depends on tra erruentranon of vinyl chloride monomer va;or. f3 ucc 059491 Work Practice Guidelin s PPG Industries has work practice guidelines used at its own plants to reduce exposure to vinyl chloride monomer during manufacture, storage and loading. Portions of the guidelines are reproduced here. Of course, some PPG practices may not be applicable to individual customer operations. Copies of the PPG work practice guidelines are available from the tech nical service staff of PPG Industries' Chemical Division. Copies of the OSHA standard, "Ex posure to Vinyl Chloride," are also available on request. Users of vinyl chloride monomer should observe the requirements of the appropriate regu latory agencies. I. Labeling and Posting A. Signs 1. Entrances to the regulated areas* shall be prominently posted with legible signs bearing the following: DANGER! CANCER-SUSPECT AGENT AREA AUTHORIZED PERSONNEL ONLY 2. Areas where hazardous operations are performed or where an emergency currently exists shall be posted with legible signs bearing the following: CANCER-SUSPECT AGENT IN THIS AREA PROTECTIVE EQUIPMENT REQUIRED AUTHORIZED PERSONNEL ONLY B. Labels for Monomer Containers Vinyl chloride monomer in container; or vessels located outside the regulai area shall be labeled as follows: VINYL CHLORIDE DANGER! EXTREMELY FLAMMABLE LIQUID AND GAS UNDER PRESSURE CANCER-SUSPECT AGENT HARMFUL IF INHALED MAY POLYMERIZE VIOLENTLY UNDER FIRE CONDITIONS OR LOSS OR REMOVAL OF INHIBITO Keep away from beat, sparks and open flame. Keep container dosed. Use with adequate ventilation. Avoid breathing vapor. Avoid contact with skin. Keep cylinder out of sun end away from heat. Container should be grounded when being emptied. Never drop cylinder. FIRST AID: If inhaled, remove to fresf air. If not breathing give artificial respiration, preferably mouth-tomouth. If breathing is difficult, give oxygen. Call a physician. IN CASE OF: Fire--Use water spray, dry chemical, or carbon dioxide. Spill or Leak--For small spills, evacuat area and permit to evaporate. For large spills or leaks, evacuate area. Dike or flush to ground and let evapo rate. Do not flush to sewer because of explosion hazard. Wear suitable respira tory protection. C. Waste Material Waste material removed from regulated area in closed containers for disposal shall have the following label: WASTE MATERIAL DANGER! MAY CONTAIN VINYL CHLORIDE MONOMER EXTREMELY FLAMMABLE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT UCC 059492 '"Regulated area" means an area where vinyl chloride concentrations are in excess of the permissible exposure limit. 14 D. Equipment Process equipment materials and clothing contaminated with vinyl chloride monomer shall not be re moved from a regulated area unless it has been purged or placed in closed containers bearing the following legend: DANGER! CONTAMINATED WITH VINYL CHLORIDE MONOMER CANCER-SUSPECT AGENT II. Apprisal of Employees Each employee working in a regulated area shall be apprised of all known hazards, the consequences of over exposure, appropriate emergency procedures, proper conditions for safe use and precautions to prevent ex posure to vinyl chloride monomer. Each plant shall have prepared an operations manual detailing procedures for performing the work which con tains specific safe work practices. These practices shall not contain in herent steps that result in exposure of the employee. III. Medical Medical surveillance shall be required or made available to workers covered by this Work Practice Guideline no less frequently than every 12 months. For employees who have worked over 10 years, this period shall be every six months. This medical program shall be considered the practical mini mum and these examinations should be reviewed every three years for revisions and supplemental testing where indicated. IV. Personal Protective Equipment and Clothing A. Respiratory Protection 1. General When the limits of exposure pre scribed on page 13 under Toxicity cannot be met by limiting the con centration of vinyl chloride monomer in the work environment through feasible engineering means, the plant must establish and enforce a program cf respiratory protection detailing the required protection of each job classi fication. 2. Non-Routine Operations The requirements set forth in this sec tion shall apply for non-routine opera tions such as brief exposure to con centrations as a result of maintenance or repair activities, emergency situa tions. or other short-time, non-standard work routines. A respiratory protection program meeting the general require ments outlined in the American National Standard, Practices for Respiratory Protection. Z88.2-1969 shall be estab lished and enforced. This program shall include instructions on the selection, fitting, use. testing for leakage, clean ing and maintenance of the respiratory protective device. 3. Vessel Cleaning. Draining. Charging or Maintenance a. Where employees are engaged in cleaning, charging or maintenance inside vessels, respiratory protection shell be worn at all times. Where the concentration of vinyl chloride monomer inside the vessel has been purged below 25 ppm. and there is adequate oxygen content to support life, an approved chemical canister mask shall be worn. Where the concentration of vinyl chloride monomer inside the vessel is below 10 ppm, a chemical cartridge respirator, which provides a service life of at least 1 hour, can be worn in lieu of the canister mask. b. Where the concentration of vinyl chloride monomer cannot be brought below 25 ppm, the employees shall wear a demand or continuous flow or self-contained respirator (Type C per OSHA standard page 35897). c. Employees making the first break into a process line, storage line or vessel that contained or contains vinyl chloride monomer shall wear respira tory protection appropriate to protect me employee from exposure to vinyl chloride monomer. 4. Routine Operations a. Workers loading or unloading tank cars, tank trucks, barges, ships, filling cylinders and other such similar opera tions where the facility does not have a closed system for vapor equalization, shall wear Type C respiratory protec tion during the above-mentioned operations. b. Where there are loading and un loading operations which incorporate equalization lines. Type C respirators shall be located in the immediate area and worn in the event of spillage, leaks or emergencies. Only those employees properly protected with Type C respiratory protection shall attempt to correct an upset condition or emergency. c. Employees engaged in loading, unloading and production shall have on their person a chemical cartridge respirator to be used for escape purposes. d. Employees who collect samples for quality control purposes shall wear respiratory protection consisting of a chemical cartridge(s) type during the period when the sample is inserted and removed from the sampling line. Respiratory protection consisting of a chemical cartridge type shall be worn when gate and globe valves are operated. e. Employees who monitor the work place air shall have available appro priate respiratory protection in the event of leaks in equipment. These employees shall wear the respiratory protection when levels being measured exceed the permissible limit. uoc 059493 Self-contained breathing apparatus. 8. Clothing 1Y Protective gloves, footwear or foot coverings, and protective head cover ing and protective eye wear shall be provided for use in regulated areas. This protective equipment shall be worn during maintenance and cleaning operations on or inside previously purged vessels, pipes, pumps and valves not removed from the regulated area. 2) For vessel cleaning, maintenance and changing charges, protective clothing shall be worn to prevent skin contact with liquid vinyl chloride monomer or other materials containing vinyl chloride monomer. 3) Employees making a break into a closed system line which contains or contained vinyl chloride monomer or other materials containing vinyl chlo ride monomer shall wear protective clothing. V. Work Practices A. Emergency Procedures Specific emergency procedures shall be prescribed. The procedures shall be readily available, in writing, to the employees. The employees shall be familiarized with these procedures, and trained and rehearsed in their application. B. Engineering Procedures An engineering review procedure shall be established to incorporate design changes where feasible to minimize sources of vinyl chloride monomer vapors from processes, loading, un loading operations and maintenance procedures that contribute to employee exposures. Where local exhaust venti lation is used, it shall be designed and maintained to prevent the accumula tion of or recirculation of vinyl chloride monomer vapor into a non-regulated area. Sample collection ports shall be so designed that during the sample collection period, the sample container is part of a closed loop system. Valves shall be located as close as practical to the end of the disconnecting line. Valves shall be located where their frequent closings are necessary to isolate equipment. Valves shall be made of high-quality type to prevent leakage of vinyl chloride monomer or liquid streams containing vinyl chlo ride monomer. Blow-down and purge lines from equipment shall be designed to return to the process or to discharge to a point remote from employees' work location. C. Laboratory Procedures 1) All quality control testing and analyses shall be performed in a laboratory equipped with a chemical laboratory hood having a capture velocity adequate to collect vinyl chloride monomer vapors under con ditions prevailing in the laboratory. The discharge from the laboratory hood shall be designed so that vinyl chloride vapors do not reenter other nonregulated areas. 2) All full sample containers (bombs) shall be stored inside the laboratory hood pending analysis. Sample bombs empty or practically empty of liquid shall not be stored in the laboratory unless the storage space is properly ventilated and under negative pressure. Sample bombs may be stored outside the laboratory building provided the stor age location meets safety requirements. 3) Analytical test instruments such as a gas chromatograph, that are located inside the laboratory but outside the laboratory, hood, shall have their purge and bypass lines discharge into the laboratory hood. 4) All quality control sampling con tainers (bombs) shall be periodically checked to assure the integrity of the valves and for leakage. Screw caps shall be provided for all sample bombs and used when the bomb is not in ' service. 5) No glassware containing vinyl chloride shall be removed from the laboratory hood. D. General Housekeeping 1) To prevent airborne contamination and accidental skin contact with vinyl chloride monomer, emphasis shall be placed upon periodic inspection, prompt repair of equipment and leaks, and proper handling, storage and dis posal of materials. ucc 059494 16 2) An initial air monitoring survey and atmospheric sampling tests shall be made in accordance with applicable standards. Thers shall be periodic tests for leaks at pumps, valves and flanges and for emission of vinyl chloride monomer. The frequency of these tests shall be such to insure the integrity of equipment and ache'ence to proper work practices. 3) For waste material and contami nated equ pment -.and; ng. see Section I (C) and (D) on Labeling and Posting. E. Special Precautions Vinyl chloride monomer is a gas at ambient temoerat.ires. Therefore, waste materials, equipment and otner sources of the monomer in closed containers shall net be placed in areas of exces sive temperature cr surlient where build jp of interna! p'essure may result in rupture of the corta ner. fire or explosion. F. Vessel Entry 1) A vessel entry procedure shall be developed. Employees shall be famili arized with the procedure in writing, and shall be trained ar.d rehearsed in the techniques provided for in the procedure. 2) Atmospheres witnir. the vessel shall be purgec tc w here vinyl chloride monomer contained therein is below 25 ppm and the oxygen content con tained therein is sufficient for support ing life. Where either the vinyl chloride monomer concentration cannot be reduced balow 25 ppm or where there is insufficient oxygen cr where other toxic materials may be present in concentrations dangerous to life, an air-supplied respirator (Type C) and protective clothing, as stated in Section l\ of this Work Practice Guideline, shall be provided by the plant and used by the employee. In vessels which have been purged to oeiow 25 ppm, resp rarer.' protection outlined in Section I /A3 shall apply. 3) All piping to ano from the vessel shall be b'arked cr otherwise isolated pr.or to ertr.'. G. Blow-Down Procedure Whenever any equipment which con tains or contained vinyl chloride monomer is to be purged or blowndown, there shall be a written pro cedure established to prevent the worker from being exposed. This can be accomplished by returning the blow-down stream to the process through equalizing lines or locating, the discharge point remote from the employee. If these systems are not feasible. Section IV of this Guideline shall be followed. H. Tank Car. Tank Truck. Barge and Ship Loading and Unloading Each unloading line and each vapor equalizing line shall be equipped with vent connections permitting, at the completion of unloading, pressure to be vented, and the hose purged with an inert gas back to the process or to a remote point from which employee exposure will not result. VI. Sanitation A. General Storage or consumption of food, storage or use of containers of bever ages, application of cosmetics or smoking are prohibited in regulated areas. B. Showers and Hand- Washing Facilities Showers, hand-washing facilities, and soap and water shall be available to all vinyl chloride workers. C. Clothing Clothing saturated with vinyl chloride monomer or with other process streams containing vinyl chloride monomer shall be promptly removed and re placed with uncontaminated clothing. VII. Monitoring and Record-Keeping Requirements A. Workplace Areas 1) Concentrations of vinyl chloride monomer in the regulated area shall be monitored at strategic sampling points. Adequate summary records of these concentrations shall be main tained and held available for inspection for a period of 30 years. 2) a. Sampling frequency and patterns shall be adequate to represent the regulated area environment and to demonstrate proper work practices and the integrity of the equipment, b. Vessel environments shall be periodically monitored at frequent intervals for vinyl chloride monomer concentrations during the times they are occupied by an employee. Sum mary records of these measurements shall be maintained for 30 years. 3) Where the manufacturing process is located out-of-doors, a sampling station should be located downwind of the operations. Multiple sampling points may be necessary. 8. Personal Monitoring 1) Sampling shall be of such fre quency and pattern as to represent levels of exposure of employees to vinyl chloride monomer. Provisions set foah in the OSHA standard for vinyl chloride monomer shall be followed. Summary records shall be maintained for 30 years for all sample schedules to include the sampling data, analytical methods, type of respiratory protection in use (if applicable) and the concen trations of vinyl chloride monomer. Job summary records shall be main tained so that they may be classified by employee. 2) Each worker shall have access to the sample results as they pertain to his occupational exposure. 3) Within ten working days after monitoring which discloses that any employee has been exposed, each such employee shall be notifed in writing of the results of the exposure measurement. An evaluation of the incident shall be made and corrective action outlined. ucc 059495 Handling antf'Unloading In many handling and unloading steps, there are potential points of exposure to vinyl chloride monomer. Consult with the technical service staff of PPG Industries' Chemical Division regarding where monomer unloading exposure points may be in your plant. Check also for other exposure points tr.at are peculiar to individual plant operations. Handling spills and leaks If the concentration of vinyl chloride vapor in air exceeds 3.6?b by volume, the lower limit of the explosive range, persons snould not enter area of spill or leak except for a rescue. Take care of a leak or spill immedi ately. Shut off or remove any possible source of ignition. Keep people away and do not permit smoking. Handle small spills by evacuating the area and lettirg the liquid evaporate. Dike the liquid from a large spill and let it evaporate. Do not flush vinyl chloride into a sawer because it may create an explcsion hazard. Spilled vinyl chlo ride should not be deliberately ignited. Invisible leaks can be detected by using a soap solution or by instruments; never use a halide lamp because of the fire and explosion hazards. If it can be done without personal risk, shut off a leak. Persons talcing care of a leak or spill, or making a rescue, should use selfcontained or air-supplied breathing apparatus and should wear sparkproof shoes and use spark-proof tools. A person contacted by vinyl chloride liquid should take a bath promptly and discard contaminated clothing and shoes. Unloading tank cars If tank car valves are defective or leaking, do NOT unload. Telephone the PPG Chemicals plant at Lake Charles. Louisiana, 318-882-1200. Spotting Car Spot tank car accurately on level track. Set car brakes and block wheels with standard rail damps. Unless car is protected by a closed and locked switch or gate, attach a derail to open end of track. Place caution signs complying with DOT regulations on track or car to give warning to persons approaching car from open end(s) of siding. The signs and derail must be left in place until after car is unloaded and disconnected. PPG tank cars are equipped only for top unloading. The car type is DOT Class 112A-340W. Jhe cars have a net weight capacity of 180.000 pounds corresponding to a nominal capacity of 26.000 gallons. Workmen unloading shipments should wear goggles and protective clothing; that is. garments suited to the partic ular situation and probable extent of exposure. If unloading procedures--particularly connecting, disconnecting and sam pling--release vinyl chloride vapors in the work area, workmen should use proper respiratory protection (see page 15, PPG Work Practice Guide lines, Section IVA2), The car should not be left unattended while being unloaded. Tank car ,\a--,mg and dera.I. 19 Wheel chock for tank cars. Preventing Ignition Static electricity must be dissipated to minimize the fire hazard. Connect grounding wire between the car tank and the unloading line. (See grounding arrangement diagram below.) Also, the car tank should be grounded as well as the rail under the tank car. Flanged joints in piping should be bonded by jumper cables. Welded pipe connections are preferable. Use a commercial meter for checking ground integrity. All wiring and electrical equipment should be explosion-proof. Class 1, Group D. No flame- or spark-pro ducing devices or smoking by per sonnel must be allowed in the area. Follow federal, local and insurance regulations. A fire hose should be available to cool the car tank and surrounding equipment in case of fire. Additional information appears in Manual Sheet TC-4 on "Unloading Flammable Liquids from Tank Cars," published by the Manufacturing Chemists Association. 1825 Connecticut Avenue, N.W., Washington, D.C. 20009. Grounding Arrangement Welded pipe connections are preferred for dissipating static electricity. Oi*gr*m courtesy Manufacturing Chtmitt* Alteration 20 Check for ground integrity. ucc 059498 Check Before Unloading Check all car va'ves to Hake sure they are closed. Check .-ai ves on the pipirg from storage tar < :o process to make sure they are clc sed. Check the vinyl chloride monomer concentration to make sure there arena ^visible leaks from valves. V/ear respirator protec tion if there is ary .eaxage. Take care of leak as recomme.ncec on page 19. Check stcrage-tsK Ie/e to make sure there is suff c:en: rcorr fcr the car's contents. T~e ?FG tank car is equipped w:th a gage red assembly (see diagram of tark car finings below) for measuring the le/e. c~ vmy: c.nlcrice. To prevent exposure cf v.or<e-s to vinyl chloride ncncmer vapor, this procedure has been m oc fied by con necting a "bull's-eys" sicnt ng dev.ee to the end of the gage red. t permits observing liquid v n.l c nitride ncncmer in a system mat is o.osec at the inspection site. Tea gas f owing cut the bull's-eye is p pad mo tne re covery system. A 2-inch valve ;s ns:a! ec vertically on the vapor oadcmg connection and two 3-inch valves or me liquid un loading outlets, which ere over educ tion pipes. Users nay reduce the vapor line valve to 1 men provic ng vapor flow is sufficient to nai Main pcsicve pressure near the e.nc of u.oloacing. Both liquid outlets can oe used to speed unloading if desirec. The vapor padding connection should be vented to tne vapor at the top of the storage tank (see unloading diagram). The thermowell do ms fitting covers a closed system filled with antifreeze. A thermometer can be inserted in the %-inch opening to obtain tne tempera ture of tha vin/l oh.or de v.nen cesired. Vinyl Chloride Monomer Tank Car Dome Fittings ^ *,! ' -4-' TV -Tbs f.'easure level of vinyl chloride monomer Imuid m tank car with gage rod assembly. 0 d) d) 0<e* SeM Vapor 1- Gogo rod oooombty, 2. liquid unteodirtf volvo. 3- Vopov podding votvp- 4. Liquid tmlooding volvo. 45-. TShotlromtyortoooiioll.f vdvf 7. Ttttinp tub*. Tank Car Unloading Station For Vinyl Chloride Monomer =AV3= -gll vocovifi to 50 poiQ. -10s* to 150*F Sampling Check contents cf tank car by sampling before unloading to verify that con tents of car are vinyl chloride and meet required specif cations. Semples are ta<en in stainless steel pressure bombs tnat meet the require ments of DCT Regulation 3B-400 and are dedicated to vinyl chloride service. All p pe connections and valves at the samplirg pc n: should be as close together as pcssicle to minimize the quantity cf v.m. I chloride monomer that must be vented before removing the sample bomb from the system. The pipe leading from the sampling ocmb is part of a closed loop system, it .s connected to a common vent manifold leading to the refrigerated recovery system cr to the stack system, f this cannot be cone, an alternative s to discharge the vent line no less than 12 feet *rc m the operator, who snould have room, to stay upwind no matter what tne wind direction may oe. A suitable breathing device must be used duri-g sampling if measure ments cf vin.l chloride monomer con centration nave indicated that expo sure is possible. An alternative arrangement has piping and valves fcr two evacuated sampling bomfcs: on a for collecting the sample; tne other for :c .letting the bleed-off. The operator sh odd wear long sleeves and gloves tc p-otect him from possible contact with residual liquid vinyl chloride monomer when he removes toe bomb from the sampling position. Liquid samples should be taken only through the gags rod assembly fitting. T. Remove hoc d from gage rod assembly. 2. While hdicing rod. release latch. CAJTiCM; Vnen ^leasing latch, do rot stand cirect y over rod because me car vapor pressure could make the r:c rise 'ap.d y :n:e the latch is reieaseo. 3. Set rod to desired level in car. I n r e center of tne ctner fittings is a scr.ng-lcacec. safety relief valve set Pressurizing Car Checking Unloading Progress PPG ships tank cars of viryl cMohde filled with liquid up to .10 more than 86% of the water we'g-t capacity of the tank. Vinyl chlori de vaocr occup >es the space above the liquid. Air or oxygen must not be inroducec during unloading or storage tc prevent fcrr-ation of a flammable mixture or cram a* ture polymerization. ?L'ge a.I lines thoroughly with nitre oen before rock ing up. Use nitrogen w th a maximum of 10 ppm oxygen, Nit'ocen purging can be minimized by sealing the i ne and alternately pressurizing witn nitro gen and bleeding off tre nitrogen tc a remote location or tc a recovers/stem or incinerator. Remove the threaded pipe plugs on the liquid and gas valves cautiously and connect the liqu d jr'oadnc line and the vapor padding lire see un loading diagram). The .acor pressure is needed to prime the tentrfuoal forwarding pump, if ore is used. To reduce pressure drop, locate the ou.mp as close to the tank ca* as possx'a. Some installations have a ccmoresscr on the vapor line from the storage tank Start unloading by slowly opening re vapor padding connection valve to tr.e car. If it is necessary to dis continue unloading for any reason, c ose all valves tightly and disconnect si unloading connections. Toe lines leading from the unloading connection valve and the padding connection valve should be purged v.ith nitrogen so that the vinyl chloride r-or oner vapor in those lines is trans ferred to the recovery system. Check the storage tank frequently to determine when the tank car is almost empty. Completely unload the tank cer; :t should not be used for storage. A pressure gage on the unloading line is the best way to indicate when all tre l quid has been emptied from the car. in addition to the pump. In wa'm climates, a compressor may be used i alone without a pump, but in cold weather a pump is usually reeled-- with or without the compressor--to facilitate unloading. The vapor pres sure used for piadding should rot exceed 225 psig. Ne^eraoply heat to accelerate the unloading of a vinyl chloride tank car. To obtain flexibility in the unloading system, either stainless steel hose on steel pipe with flexible joints can be used. The flow of vi-y! crlodtie hon the tank car shouid be regulated oy a valve in the transfer lire, '.f toe dis charge rate suddenly, tecorres tco great an excess flow coeck valve in the tank car will close. To re-ooen triis valve, close the untcac ng connection Fjrg:ng line with nitrogen. valve until the pressure is equalized. I ucc I 059501 -sr.Tj vapor caedmg Me. 23 Connecting liquid unloading line. After Car Is Emptied Stop the forwarding 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 transfer line. The lines leading from the unloading connection valve and the padding con nection valve should be purged with nitrogen 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 leak as recom mended on page 19. Do not allow 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 "DANGEROUS" placard on the car so that it reads "DANGER OUS--EMPTY" (see photo). IMPORTANT Leave at least 10 psig of vinyl chloride vapor pressure in the empty tank car being returned after closing and seal ing all openings. The pressure is necessary to prevent air from entering the car. Notify PPG Chemicals immediately if any valves are defective or leaking; telephone the manufacturing plant at Lake Charles. Louisiana 318-882-1200. After tank car is emptied, reverse"DANGEROUS" placard so that it read*"DANGEROUS--EMPTY." Car 90-ton TANK CAR DIMENSIONS Water Capacity 26.000 gal. Length Over Strikers' 50'5' Overall Height2 15*5" Height to Valve Outlet1 14'1 - Extreme Width3 10'6%* 'Add 2'7'A* for length over center line of coupler knuckles, heights are for empty cars and are measured from top of rail; heights of loaded cars may be as much as 4* less. *Width over grab irons. Note: Height to manway platform is 6" to 10" less than height to centerline of valve. Overall Length 48'7* TANK TRUCK DIMENSIONS Height to Top of Relief Valve 10'8* approx. Overall Width 96* Leave at least 10 psig of vinyl chloride vapor pressure in the empty tank car. 24 ucc 059502 1 Unloading tank trucks Tank trucks deliver shipments usually within a 100-mi!e rac'us of Pauistoro, N. J. The tank trucks have a ret weight capacity of 40.000 pounds correspond ing to a nominal capacity cf 5.200 gallons. The trucks are unloaded on either side from the bottom near the back end. Since the sizes cf the liquid line connections (3 inches) and vapcr padding connections ,2 inches) are the same as for tank cars, any user receiving tank car shipments can take a tank truck shipment so long as the truck can get close enough to the unloading site. If not, a afferent length of pump suction line cr vapor padcing line would be needed. Users nav re duce the vapor padding connecton to 1 inch, providing vapcr f,ow is sufficient to maintain positive pressure near end of unloading. Personnel should not sit in the cab while unloading, and tne unloading should not go unattended. Workers unloading shipments snculc v.ear goggles, protective cloth nc and pro tective respiratory equipment if needed. Spotting Truck Shut off the truck engine. If fo: some reason the tractor must be separated from the trailer, do this tefC'e making any connections anc place a "norse" that is strong enough oncer the front end. Don't rely on the sudport w reels to hold the load. Set the ora<es anc chock the wheels. Locate the vinyl chloride truck so as to protect it from collision with a passing vehicle. Allow no vehicular traffic in the area until unloading is csmpleted. If this cannot be cone, minimize and control traffic by terrporar/ roadblocks. ucc 059503 25 - Preventing Ignition Static electricity must be dissipated to minimize the fire hazard. Connect a grounding wire between the trailer tank and the unloading line. Also, the truck chassis should be grounded. Flanged joints in the unloading system piping should be bonded by jumper cables. Welded pipe connections are preferable to flanged. Use a commercial meter for checking ground integrity. All wiring and electrical equipment snculd be explosion-proof. No flamecr spark-producing devices or smoking fcy personnel must be allowed in the area. Follow federal, local and insurance regulations. A fire hose should be available to cool the trailer tank and surrounding equipment in case of fire. Check Before Unloading Cneck all tank truck valves to make sure they are closed, also check valves on the piping from storage tank to process. The valve at the truck end of the liquid line hose should have been closed after the previous delivery. Because liquid vinyl chloride monomer has a high coefficient of expansion, the liquid line to the storage tank should have a safety relief valve no smaller than one inch, preferably located close to the storage tank. Check the storage tank level to make sure there is sufficient room for the truck's contents. Inspect the pump, vapor line and liquid line hoses or flexible-joint piping for any defects including leaks. Ground the tank truck. A fire hose and hydrant should be close by in case of fire. Unloading Vinyl Chloride Monomer From Tank Truck sore* (Liquid) ucc 26 059504 Store the hose or flexible arm off the ground on a suitable support. The coupling covers should be in place to keep out dirt and moisture. The short spool piece at the end of the hose should always remain with the hose. Do not substitute a different piping section for it. The spool piece is purposely short to minimize its air content and avoid the need for nitrogen purging. All emptied sections of the system should be clean, dry and free of air before monomer is introduced. If nitrogen purging is necessary, it can be minimized by sealing the line and alternately pressurizing with nitrogen and bleeding off the nitrogen to a remote location or to a recovery system or incinerator. If the liquid monomer in the truck is cold, its vapor pressure may be quite lo -v. Hook up the coupling of the vapor padding line and ground it. Make sure the closure is tight. If the vapor pressure in the truck drops below 10 psig. bleed pressure from the storage-tank vapor space into the truck vapor space. Aside from the safety aspects, the storage-tank vapor space must be practically free of oxygen and other contaminants to avoid incurring charges for delaying the truck and purging it after the truck returns. If a vapor compressor is used in addi tion to. or instead of, a pump, the compressor must not be capable of delivering over 100 psig. The safety relief valve on the truck is rated at 150 psig. Hook up tha vapor padding l.-e. Unloading Procedure 1. Hook up the coupling of the liquid line and ground it. Make sure the closure is tight and the spool piece bleed valve is closed. 2. The coupling of the vapor padding line has already been hooked up and grounded. Open valve from vapor space on storage tank. 3. Slowly open the truck and hose valves of the liquid line. 4. Start the pump and/or vapor com pressor. If the excess flow valve in the truck liquid outlet closes, shut the outlet valve until the pressure is equalized. The flow of vinyl chloride from the truck should be regulated by a valve in the hose line, preferably the valve closest to the storage tank. The truck can be unloaded at a rate up to 350 gallons per minute. Keep a posi tive pressure on the truck vapor space to avoid the possibility of pulling in air and to prevent pump cavitation. 5. A change in the sound of the pump, as well as a pressure drop on the gage, indicates when the liquid has been completely unloaded from the truck. Do not try to pump out vapor from the truck, because this can produce a vacuum and suck in oxygen from the air. If the vapor pressure in the truck drops below 10 psig. bleed pressure from the storage-tank vapor space into the truck vapor space. Hook up the liquid unloading line. Check pressure on emptied tank truck to make sure at least 10 psig of vinyl chloride vapor pressure are left. ucc 059506 I 28 After Truck Is Emptied 6. As soon as the liquid has been emptied from the truck, shut down the pump and/or compressor. Close the liquid valves on the truck and on the hose. Carefully bleed vapor from the liquid line spool piece (see diagram on' page 26 and photo at right) to the storage-tank vapor space. 7. When both liquid and vapor pres sures are gone, disconnect the liquid line from the truck and install the blind coupling covers. Shut off the bleed valve on the liquid line spool piece. 8. Likewise, disconnect the vapor line from the truck and install the blind coupling covers. Shut off the bleed valve on the vapor line spool piece. Use respiratory protection. 9. Remove electrical grounds. 10. Remove chocks to release the truck. Check emptied tank truck for oxygen with a portable meter. 29 Unloading barges and ships Procedures for unloading vinyl chloride monomer from barge and ship cargo tanks are essentially the same as for unloading tank cars. There is, how ever, more variation in facilities and conditions at customers' plants that may require modifications of unloading methods and equipment. PPG tech nical service engineers are available for consultation on particular bargeor ship-unloading problems. Facilities for unloading barges and ships should have self-contained breathing apparatus available for per sonnel and instruments for monitoring vinyl chloride vapor concentrations. Construction materials Aluminum and its alloys must not be used in equipmenfto store or handle vinyl chloride because explosive aluminum chloroalkyls can be formed. PPG's vinyl chloride is made from ethylene and contains no detectable amount of acetylene. However, vinyl chloride made from acetylene by an older process contains traces of acetylene that could react with copper or its alloys to form explosive copper acetylides. It is not safe to use such vinyl chloride in processing equipment containing copper or brass. Carbon steel is the recommended construction material for storage tanks, pumps, valves, fittings and pipe to handle vinyl chloride. Although stain less steel is quite satisfactory, it is not necessary. Cast iron or ductile iron should not be used because equipment fracture or breakage could possibly permit a major spill. Equipment and piping should be able to withstand working pressures of 150 psig. If a system containing vinyl chloride monomer may be closed at any time, it should have duplicate relief valves. Valves and fittings should be of a type that does not require lubrication. Many lubricants are attacked by vinyl chloride and should not be used. Eccentric-type plug valves are avail able that tighten further as the seats wear out. Storage tanks Vinyl chloride has indefinite storage life and does not polymerize when kept in contact with ferrous materials in the absence of air or oxygen, water, tight and excessive heat. Storage areas should be selected to comply with local codes or authorities. Such organizations as the National Board of Fire Underwnters. the Factory Insurance Association and the National Fire Protection Association provide information about site selection on request. Locate a vinyl chloride storage tank in a segregated area away from major process units. It should be engineered as a Class I, Group D, Division I area and treated as such. Process units such as furnaces or reactors, which have higher than average fire or explosion hazards, should be situated as far from a vinyl chloride storage tank as practical. To take care of spilled liquid in the event of a tank rupture, adequate dikes and drainage should be con structed (see photo). Storage tanks should be constructed of materials recommended above, in accordance with the ASME code for unfired pressure vessels. They should be designed to withstand full vacuum or a working pressure of 100 to 150 psig. However, vapor-recompression or refrigerated storage tanks can be designed for lower pressures. Allwelded construction is recommended. Tanks should be painted with white or other heat-reflective paint. The installation should include a waterspray system in case of fire. To prevent a buildup of static elec tricity while a tank is being filled, the liquid inlet line should extend to the tank bottom. The stand leg should have a hole in it near the top of the tank as a vacuum breaker that prevents blowback. The tank and filling equip ment should be grounded against static electricity and lightning. Resis--tance to ground should not exceed 25 ohms. 9 r.ss + - j9\ * Spray nozzle for cooling outside of storage tank in case of fire. A dike is needed to contain spilled liquid in case a tank should rupture. ucc 059508 30 iquid outlet lines to process should e equipped with check valves to .revent contamination by backflow, adequately sized pressure-relief valves nould be installed on top of a storage ank. To allow for periodic removal and nspection of the valves, they should ,e installed preferably with a 3-way !ug cock in the line that can block ff first one, then another valve from ie tank. idicarors of liquid monomer temperajre should be installed near the tank :ottom to permit observation from the ground. Vapor pressure gages should e connected to the top of the tank : jt the indicator should be located ear the ground. Tanks should also ave a liquid level gage with groundeve! readout. The level should not xceed 90% of the tank's capacity. Before a tank receives vinyl chloride monomer, the tani< should be cleaned and purged with a dry inert cas until free of oxygen (see photo). The oxygen content must initially be no more than 1.000 ppm by volume. Check tanks regularly for the presence of polymer. Tanks in vinyl chloride service should not be used to store other mste-ials. After a storage tank has been p'aced in operation, follow'standard procedures to prevent oxygen from er.ter.nc. For example, when tank cars cr ether shipping containers are unloaded, they could vent oxygen back to the storage tank, if their vapor space was of poor quality. The tanks must be inerted to` remove oxygen, preferably by alternately pressurizing and depressurizing with nitrogen. Horizontal cylindrical tanks are used at ambient temperatures tc hole up to 50.000 gallons of vinyl chloride: fGr higher capacities, spheres are preferable. Although vinyl chloride monomer is sometimes stored as a liquid at atmo spheric pressure by means of refrigera tion, it is usually stored under pressure. The actual pressure inside a storage tank depends on the ambient tempera ture (see graph on page 10). For ex ample. between the freezing point of water and 25C (77F) the internal vapor pressure varies from 1293 to 2943 millimeters of mercury or from 25 to 57 psig. Therefore, every poten tial leak site should be checked periodically. Ail vessels in the vinyl chloride monomer system should be interconnected by pressure equalization lines, which are connected to a refrigerated vaporrecovery system. The term, "vessels," includes storage tanks, shipping con tainers and processing equipment. Since it is impossible to condense 100% of the vinyl chloride monomer vapor, the inert gas stream from the refrigeration unit will contain some vinyl chloride monomer. Reading tank temperature indicator. Testing storage tank for oxygen with a port able meter. ucc 059509 Transfer lines To empty a line of vinyl chloride monomer, take care to bleed it off safely either to a condensing system or to a remote location. Then blow out the line with nitrogen. Before any maintenance such as welding is per formed on a long transfer line, steam ing should be continued for several hours. The line will have to be reamed if polymer has formed. Relief valves on transfer lines should be vented to the top of a vinyl chloride monomer storage tank. To prevent the buildup of static elec tricity, pipe connections should pref erably be welded. If flanged connec tions are used, they should be bonded with jumper cables. Waste disposal Waste contaminated with vinyl chloride monomer is toxic and a potential fire hazard. The handling of vinyl chloride monomer waste must be done with strict adherence to the OSHA standard. "Exposure to Vinyl Chloride." Vinyl chloride monomer waste should not be permitted to enter sewers or drains because potentially explosive vapor concentrations can collect. Waste disposal depends largely on the surroundings, weather and the type of emergency that requires the disposal. Observe all federal, state and local regulations regarding health and pollution. Monitoring exposures Equipment for determining concen trations of vinyl chloride monomer vapor in workplace air can be divided into three classes: (1) personal. (2) fixed area and (3) portable area monitoring. 1. In the method that NIOSH (National Institute for Occupational Safety and Health) has been using for personal monitoring, air from the worker's breathing zone is drawn through a tube that can be clipped to his shirt collar. Suction comes from a battery-operated pump that can fit into his shirt pocket or over his belt. Acti vated charcoal in the tube traps the vinyl chloride while the pump runs for 15 minutes. For analysis, the vinyl chloride is removed from the charcoal with carbon disulfide and is subse quently determined on a laboratory gas chromatograph having a flame ionization detector. An alternative method gaming popu larity because of its speed is an air bag strapped to a worker's back. A battery-operated pump attached to his person draws vapor into the bag. Injecting a needle into the bag obtains a sample for gas chromatographic analysis. 2. Fixed area monitoring uses either a gas chromatograph or infrared spectrophotometer. A suction pump near the instrument draws samples through long tubes ending at remote, fixed-site pickup points, commonly ten or twelve points. An automatic programmer provides sequential analyses of the multiple sampling points for cycles such as several minutes each. The instrument can be equipped to sound an alarm when a preset exposure limit is exceeded. 3. Portable instruments are used where fixed area monitoring is imprac tical. They can also serve for detecting leaks and for making rapid surveys of areas. The various types of portable instruments used include the infrared spectrophotometer, flame ionization instruments, and instruments that measure total hydrocarbons, ucc 059510 Relief valve on transfer: ne is vented to i:o of storage tank. 32 Reducing Exposure to Vapors in the Laboratory - Store all sample bombs in a rack inside a fume hood. The hood should be large enough to permit doing all analyses without removing sample bombs from hood. Sample lines in and out of the chromatograph sampling valve should be piped to r,e hcod. The "sample in" line is connected to a rotameter to measure samp e flow. Thus, chromatographic samp.mg is carried out without remov ng sample bombs from hood. If the chromatograph has a thermal conductivity detecting cell, the exit gas--consisting of vinyl crlc-ice monomer vapor and the cam er gas-- should be vented to the hdoc. How ever, if the chromatograph has a flame ionization detecting system, the vinyl chloride will be complete!, fc jrred to form hydrogen chloride ard caroon dioxide. All analyses should be performed without removing sample bombs from hood. Personal monitoring device traps any vinyl chloride vapor on activated charcoal in tube. =f-serial monitoring device collect* air and . vaoor in plastic bag. Pomade area men tor no iri:r_-r=-.; ;an also be used for oerectng iea. 33 UCC 059511 Analysis Methods Of Analysis The following abstracts are taken from the methods of analyses used by PPG Industries' Chemical Division to make the determinations listed under Specification and Typical Analysis on page 9. Copies of the complete methods are available on request from PPG's technical service staff. Acidity, as HCI This method involves the determina tion of the acidity or alkalinity of vinyl chloride monomer by absorption in neutral distilled water and titration of the absorbate to a pH of 7.0 with sodium hydroxide. Iron, as Fe This method involves the spectrophotometric measurement of the color produced by the ferrous-o-phenanthroline complex. The vinyl chloride is allowed to evaporate from an alcoholacid solution, and the iron is deter mined on the resulting solution. Nonvolatile residue A known weight of vinyl chloride is evaporated to dryness, and the weight of the residue is reported as non volatile residue. Water This method involves the determination of water in vinyl chloride monomer by titration with Karl Fischer reagent. The end point is determined electrometrically utilizing a suitable "dead-stop" titra tion apparatus. Sulfur This method involves the conversion of sulfur in vinyl chloride to sulfate and precipitation as barium sulfate. Barium sulfate is measured turbidimetrically with a spectrophotometer. Acetaldehyde The reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine is the basis of the determination of acetalde hyde in vinyl chloride monomer. The reaction takes place under acid condi tions in carbonyl-free methanol solvent to form the hydrazone. The addition of a solution of potassium hydroxide produces an intense wine-rd color. The absorbance maximum occurs at 480 nm and is measured against a reagent blank. Testing for impurities in vinyl chloride monomer with gas chromatograph at PPG plant in Lake Charles. Louisiana. 34 ucc 059512 Purchasing Purchasing Information Grades PPG Industries produces only polymer* grade vinyl chloride monomer. PPG normally supplies vinyl chloride monomer uninhibited. This eliminates the need for subsequent processing to remove the inhibitor. If required. PPG will add a suitable inhibitor. Shipping PPG Industries delivers vinyl chloride monomer by ship, barge, tank car and tank truck, there are three shipping points: Guayamlla, Puerto Rico Lake Charles. Louisiana Paulsboro, New Jersey The tank trucks hold up to 40,000 pounds of vinyl chloride. Tank car capacity is 180,000-pounds net weight. Ships ordinarily hold up to 6 million pounds and barges up to 4 million pounds. PPG has a fleet of tank cars for vinyl cnlonde service only and leases a fleet of tank trucks designed and used only for delivering vinyl chloride. Tank truck shipments, normally made within a 100-mile radius of Paulsboro, N.J.. offer several benefits to customers: Lower investment Frequent deliveries by tank truck permit lower investment in inventoried material both in tank and in transit. Since smaller storage facilities can suffice, less capital need be invested. Fast Service Truck deliveries provide fast service on short notice and can supply unusual as well as usual demands. Savings on Assays and Polymerization Batch Control The Paulsboro terminal has two huge storage tanks each holding over 26 million pounds of vinyl chloride. Be cause of these tremendous quantities, the vinyl chloride monomer in these tanks is more homogeneous than material coming from smaller tanks. Dedicated Drivers Truck drivers are trained and dedicated for vinyl chloride service. They are safe drivers and maintain good community relations. Rail Track Space Savings Depending on the customer's situa tion. this advantage too can materialize. Samples and service Samples of vinyl chloride monomer are available on special request in returnable laboratory-size steel cylinders holding 5 pounds. The Pittsburgh-based technical service staff of PPG Industries' Chemical Division is available for consulting on handling, storage and use. ucc 0S9513 35 Percarbooate Initiators For Tha Polymerization Of Vinyl Chloride PPG Industries' Chemical Division supplies a line of peroxydicarbonate initiators for the polymerization of vinyl chloride, ethylene and other unsaturated monomers. These initia tors provide free radicals at consider ably lower reaction temperatures than most organic peroxide initiators. Because of their high efficiency, the peroxydicarbonates are used by com panies that produce most of the annual U.S. output of polyvinyl chloride. PPG has marketed diisopropyl peroxydicarbonate (IPP) for close to 30 years. Although many users prefer handling solid initiators such as IPP. those who find undiluted liquid initiators or their solutions advan tageous can now select di-n-propyl peroxydicarbonate (IMPP), di-sec-butyl peroxydicarbonate (SBP) ordi-(2ethylhexyl) peroxydicarbonate (EHP). Peroxydicarbonates have the same general formula: Q0 II II ROCOOCOR Advantages that IPP, NPP, SBP and EHP have over other initiators for the production of polyvinyl chloride and other polymers include the capability of the peroxydicarbonates to: Reduce Time of Batch Runs Enable fast rate of conversion during the very first hour of reaction and, until the run is terminated, the polymeriza tion rate remains high and constant Increase Production Because batch runs take less time, a much greater annual output of polymer can be produced from the same equip ment with peroxydicarbonates. Make Polymerization Easier to Control Rate of heat evolution is nearly con stant. No large exotherm occurs near end of run as with many polymeriza tion initiators that accelerate reactions near the end. In comparison with other commonly used peroxides, a peroxydicarbonate permits easier termination of a batch polymerization. Improve Polymer Characteristics Lower reaction temperatures, linear conversion rates, and less initiator residues are among the factors con sidered responsible for improving such characteristics as color, electrical re sistivity, and stability to ultraviolet light and weathering. Peroxydicarbonates are powerful oxidizing agerts. They are hazardous chemicals shipped under refrigeration and must be stored under refrigeration. Many users prefer handling solid IPP because the heat of fusion provides a safety factor; that is. the solid must melt before it decomposes. Also, pieces that have dropped are easier to pick up and dispose of than liquid spills. However, other users find the un diluted liquid forms and solutions easier to handle and prefer adding initiator to process volumetrically instead of by weight. Also, NPP, SBP and EHP are more soluble in most of the solvents used to dilute peroxydi carbonate initiators. More information Detailed information appears in a 40-page booklet, "Percarbonate Polymerization Initiators," form A-961. available on request. ucc 059514 36 ? SALES OFFICES ATLANTA. GEORGIA 30318 188 Fourteenth SL, N.W. (404) 875-9626 BOSTON (SOMERVILLE). MASSACHUSETTS 02145 100 Felltway West (617) 666-3900 CHARLOTTE, NORTH CAROLINA 28202 359 Northwest*TM Bank Building (704) 377-7631 CHICAGO (DES PLAINES), ILLINOIS 60018 NAII Building, Room 307 2600 River Road (312) 298-8390 CINCINNATI, OHIO 46237 Carrousel Towers 8075 Reading Road (513) 821-2062 CLEVELAND, OHIO 44116 Westgate Plaza Building 20325 Center Ridge Road (216) 331-4100 HOUSTON, TEXAS 77069 Champions Bank Building, Suite 520 5625 FM1960 West (713) 440-3770 LOS ANGELES (WHITTIER). CALIFORNIA 90603 15111 East Whittier Blvd. Suite 39S (213) 945-2431 MINNEAPOLIS, MINNESOTA 55416 351 Tyrol West Building 1500 South Lilac Drive (612) 544-8841 NEW YORK (WEST ORANGE, NEW JERSEY) 07052 80 Main Street (201) 736-9700 (212) 964-7910 PHILADELPHIA (HAOOONPIELD. NEW JERSEY) 08033 76 Euclid Avenue (215) 564-3390 (609) 428-7800 PITTSBURGH. PENNSYLVANIA 15222 Gateway Towers (412) 434-2358 PORTLAND. OREGON 97232 1500 N. E. Irving Street, Suite 365 (503) 233-5455 ST. LOUIS, MISSOURI 6310S 111 South Bemiston Avenue (314) 863-2525 SAN FRANCISCO (MILLBRAE). CALIFORNIA 94030 199 California Drive (415) 697-0100 SAN JUAN (HATO REY). PUERTO RICO 00918 1420 Chase Manhattan Building (809) 764-0485 For technical information on vinyl chloride monomer, contact: Organic chemical technical service Pittsburgh. Pennsylvania (412) 434-2403 Producing plants Lake Charles. Louisiana (318) 882-1200 Guayanilla, Puerto Rico (809) 835-4700 Statements and methods presented are based upon the best information and practices known to PPG Industries. Inc. but are not representations or warranties ofperformance or result, nor do they infer any recommen dations to infringe any patent or an offer of license under any patent. With respect to its product* PPG INDUSTRIES, Inc. only warrants that they conform to its quality standards. Soma of the materials mentioned above may be hazardous in nature and should be handled with care. Read the label carefully and observe and comply with all the label warnings and precautionary directions. Although these materials are not intended for household use. they, as all potentially hazardous materials, must be kept out of the reach of children. ucc 059515