Document 0JVY73mDNKq45K9zGEx6dz3GV

m% # Introduction This second edition reflects the work practice changes required by the Occupational Safety and Healtn Standard published October 4, 1974, in the Federal Register. The proce dures recommended in this manual follow the work practice guidelines adopted for PPG plants producing vinyl chloride monomer. Of course, some PPG practices may not be appli cable to individual customer operations The Chemical Division of PPG Industries manufactures vin,I c'-lcr.ce monomer at Lake Charles, Lou s.ara. and at Guayanilla, Puerto Rico The combined capacity of tr.ese t.-.o facilities is rated at 900 million pounds per year. This capacity makes PPG a major supplier of vinyl chloride monomer to producers of polyvinyl chloride resins PPG is also a major supplier of percarbonate polymerize: cn initiators used in the manufacture of polyvinyl chloride. The following pages show PPG's large-scale com mitment to vmyl chloride monome' production. ASI 000013637 1 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 -n olefins plant half-owned by PPG. :s annual capacity includes one billion :ounds of ethylene, which PPG com ines with chlorine to produce vinyl nlonde 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 tec'-nologv. PPG developed the process m tre early 1950s and commercialized it in the early 1960s. Related to PPG's vinyl chloride monomer is its production of vinylidene chloride monomer. ASI 000013638 4 1 s :cflce3fc'J tins of Qw c .try! oicf Gf rncrC'T6f j/'Ccf pressure PPG offers re East Ccas: s first Ian* ;ruCK Deliveries of vinyl crucr.ae monomer 7'ie Pautsc^ro terminal can s;^re 53 3 pounas of monCfner. ' W( ASI 000013639 5 1  HI At PPG's Lake Charles, Louisiana plant, a tank car is being loaded with Iiquio vinyl chlonoe monomer under pressure PPG has a fleet cf tank cars dedicated to vinyl chiorioe service. Norwegian vessel nas taker, on a cargo tank of Iiquio vinyl chloride mcnomer under pres sure from the PPG plant in Lake Charles, Louisiana. PPG loads Shms with up to sir million pouncs of monc -r. *'* _-r< m ~f ASI Barge racing cargo tarns of liQu.C vmyl cnlcnoe monomer unoer pressure is being Icadeo at the PPG plan: m Lake Cranes. Louisiana. From mere, the darge can travel up me Mississippi arc Ohio r.vers A barge can '-ir million pcunos Of monomer. 000013640 Storage spheres at PDG's Lake Charles. Louisiana pian; hold thousands of gallons each of liquid vinyl chloride monomer unoer pressure hor.cental storage tanns at right serve as quality control tanirs. 6 tvf. ASX 000013641 Properties Chemical Names: Vinyl chloride, vinyl chloride monomer, chloroethylene, chloroethene Chemical Formula: CH2CHCI 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, C F --13.8 +7.0 FreezingPoint. C F --153.7 --245 Flash Point, open cup, 6C F --78 --108.4 Explosive Limits, volume % in air at 25C(77F) 3.6 to 33 Autoignition Temperature. C 472 F 882 Critical Temperature. eC F 158.4 317 Critical Pressure, psia Vapor Density. air= 1 Solubility, water in monomer at 25C (77F), weight % _ 775 2.15 0.11 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 peroxiae formation due to air exposure is a slow reaction, certain peroxide product: are shock-sensitive Vinyl chlonce 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 relativei'. inactive and is more stable than m saturated or allylic compounds. Specification jnd Typical Analysis; -- - Appearance Color Acicty, as HCI. ppm Iron, as Fe. ppm (filtered sample) Nonvolatile residue. weicht 3o Water, ppm Sulfur, as SO;, ppm Acetaldehyae. ppm Acet.iene, ppm Specification clear, free of suspended matter colorless, water-white 5 maximum 0.5 maximum 0 05 maximum 100 maximun 3 maximum 5 maximum 2 maximum* Typical Analysis clear, free of suspended matter colorless, water-white <1 0.1 0 00C3 34 <1 <1 <1 *7-.s T,ax-n"jT> s s". -nous^ry stancard: "cwever, tne PPG product contains no detectable enr.cur.i cf acetone. LIQUID DENSITY DENSITY *T evnvvn it TEMPERATURE. 4*f'*ft* CnttQr$&9 *huhi |imi p*> ffwitnntf ftv | 4 9 ASI 000013643 VAPOR PRESSURE 000013644 ASI PRESSURE, millimeters mercury Fir and explosion 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 vinyi * chloride monomer may catalyza^ polymerization, which is higni^Athermic, or cause decomposing^\ which liberates toxic hyoroger. * r gas. The high purity of vinyl chlcrice must be maintained in shipment, transfer and storage. Exposure to oxygen, air or sunltgr: can also catalyze polymerization. Peroxides may also form. Toxicity The Occupational Safety and Hesiv Standard on exposure to vinyl chic* published October 4, 1974. says: "Based on the demonstratea eviae^ of vinyl chloride monomer's carcinc gemcity in three animal species tra: mice and hamsters), and the sub stantial probability that vinyl chLr.c monomer had oeen tne causal age'in the cases of liver angiosarcoma found in workers botn nere ana ac OSHA . . . published a comprener.; proposal ... to protect employees from hazards of exposure to vinyl chloride monomer." ASI 000013646 12 Stated in this OSHA standard is the following "Permissible exposure limit" cheduled to become effective oril 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 tnan 5 ppm averaged over any period not exceeding 1 5 minutes. (3) No employee may be exposed to vinyl chlorine by Direct contact with liquid vinyl cnloriae In cases where these limits of exposure are exceeded, the wearing of respira tors will be manoatory for workers beginning Apr,I 1, 1976. Until tnen, tne wearing of respirators is discre tionary for exposures under 25 ppm. Besides tne suspected carcinogenicity, vm1,1 cr.icntie monomer vapor can pro duce immediate symptoms in persons excoseo to mgn concentrations. The odor of vinyl chloride monomer is sweetish and the sense of smell can not be relied upon as a warning. High vapor concentrations may cause lung irritation, can cause dizziness and anesthesia, and may do other 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 snipped today is not inhibited. Workers should wear eye protection anc protective clothing to prevent skin contact witn tne liquid. If vinyl chloride gets on clothing or shoes, they snoulo be removed immediately. If vinyl cnlonde contacts tne skin, wasn immediately with soap and water If vinyl chloride contacts the eyes, the eyes should be washed immediately and thoroughly with water for at least 15 minutes. Get medical attention. Worriers should wear protective clothing and eye protection wnen unloaoing shipments, WA Whether or net respiratory prctect.cn is used, ana what type, oepenos on the concentration of vinyl cnloriae monomer vapor. ASX 000013647 13 1 ASI 000013648 1 W rk Practice Guidelines 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 wnere 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 :n conta.ne-s ` or vessels located cutsice tne regO^ area shall be labeleo as foiio ws: 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 INHIBITOR Keep away from heat, sparks ana open flame. Keep container closed Use with adequate ventilation. Avoid breathing vapor Avoid contact with skm, Keep cylinder out of sun and a a ay from heat. Container should be grounded ,vnen being emptied. Never drop cylinder. FIRST AID If inhaled, remove :o fres^ air If not breathing give art.ficial respiration, preferable mouth-tomouth. If breaihir difficult, g ve oxygen. Call a pr. n IN CASE OF. Fire--Use water spra,. or, c-emicai. or carbon oioxioe. Spill or Leak--For small sP'lis. evacuate area ana permit to evaporate For large spills or leaks, evacuate area Dike or flush to grouna anc let evapo rate. Do not flush to sewer because of explosion hazard Wear su'tatle resc ratory protection. C. Waste Material Waste material removed from regulates area in closed containers for d.spossi shall have the following label. WASTE MATERIAL DANGER1 MAY CONTAIN VINYL CHLORIDE MONOMER EXTREMELY FLAMMABLE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT "'Reaulated area" oiears an a-aa ,- - --? v ,'l cnicriae concentre* c~s 3^ of tne per'Tvss Die evccsure -- 14 i D. Equipment rProcess equipment, materials and clothing contaminated with vinyl shloride monomer shall not be renoved from a regulated area unless it has been purged or placed m 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 emergencyprocedures. 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 mace availaole to workers covered by- this Work practice Guideline no ;ss frequently tran every 12 months Eorempic.ees woo have worked over 10 years, this per.od snail be every six months Ins medical program shall be consicered the practical mini mum and these examinations should be reviewed every mree 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 served on page 1 3 under Toxicity cannot be met by iimitmg the con centration of vinyl chioride monomer in the -work environment througn feasible engineering means, the plant must establish and enforce a program of respiratory protection detailing the required protection of each job classi fication. 2. Non-Routine Operations The requirements set forth m 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 Resoiratory 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 shall 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 the employee from exposure to vinyl chloride monomer. 4. Routine Operations a. Workers loading or unloaqing 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 resDirators shall be located in the immeoiate 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 samcles 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 availaole 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. * Self-contained breathing apparatus. 15 1 fc Handling and Unloading In many handling and unloading steos, there are potential points of exposure to vinyl chloride monomer. Consult with the technical service staff of PPG Industries' Chemical Division regaraing where monomer unloading exposure points may be m your plant. Check also for other exposure points that are peculiar to individual plant operations. Handling spills and leaks If the concentration of vinyl chloride vapor in air exceeds 3.6% by volume, the lower limit of the explosive range, persons should 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 go not permit smoking. Handle small spills by evacuating the area and letting the liquid evaporate. Dike the liquid from a iarge spill and let it evaoorate Do net flusn vinyl c.nlorice into a sewer because it may create an explosion hazard SDiileG vinyl chlo ride snould net be delioerately ignited. Invisible leaks can be oetected by using a soap solution or by instruments, never use a halice lamp because of the fire and explosion hazards. If it can be done without personal risk, shut off a leak. Persons taking care of a leak or spill, or making a rescue, should use seifcontained 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 aiscard contaminated clothing and shoes. Unloading tank cars If tank car valves are defective or leaking, do NOT unload. Teieoncne the PPG Chemicals plant at Late Charles, Louisiana, 318-882-1200. Spotting Car Spot tank car accurately on level track. Set car brakes and Dlock wheels wun standard rail clamps. Unless car is protected by a closed and lockeo switch or gate, attach a derail to open ena of track. Place caution signs complying with DOT regulations on track or car to give warning to persons approaentng car from open end\s) of siding. The signs and derail must ce left in place until after car is umoacec and disconnected. PPG tank cars are equipped only for top unloading. The car type is DOT Class 112A-340W. The cars have a net weight capacity of 180,000 pouncs corresponding to a nominal capacity of 26.000 gallons. Workmen unloading shipments snouic wear goggles ana protecbve ciotnmg, that is, garments suitec to tre partic ular situation and proDabie extent of exposure. If unloading procedures--particular!-, connecting, disconnecting anc sam pling--release vmyl chlcrice .accrs in tne 'work area, workmen srcuia use proper respiratory protect cr isee page 15. PPG Work Practice G. celines. Section IVA2). The car should not be left unattended while being unloaoed. Tann car stop. Tank car warning ana aerail 15 vVneei crock fcr rank cars. ASI 000013651 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 m 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. .> Ground the tank car before unloading. Grounding Arrangement AoprSv^C ~3- "=e to Storage Ji Extra F>e* be Sfraffc2 /l --- -----Copoer A.r 30 t Pi f^' * ftuboer irsulat'on Flanged joints should be ooru^j cy u-rcer cables. vv sr- Aelaec pee cc''."e::.c,'S are cra'y ass.paling static eiectr.c.tv- ASI 000013652 Ground Con# or Eo-.`vier>t Check for ground ntegnty. , Check Before Un/oec ng Checx all car valves to make sure they are closed Check valves on the piping fmm storage tank to process to make ( tney are closed. Check the vinyl .once ""onomer concentration to make sure tnere are no invsible leaks ' from waives 'Aear respiratory protec. t.on ,f mere is an: leakage, take care ;f !eax as recommences on page 19. . Cnec< storage-tan* level to make s..re me'e is Suff-c en: mem for the * car's cements T-'e PPG tame car is ecumceo wim a gage rod assembly . tsee piagram of tanK car fittings below) for measuring me level of vinyl chloride. * To prevent exposure :f workers to vinyl chloriae monomer vaDOr, this * procedure has been modified by con necting a "bull's-eye'" signting device to the end cf tne gage rod. It permits Deserving liqjia vinyl chloride monomer m a system tnat is closed at the inspection site. The gas flowing out me cu;!'s-eye is pioeo into the re cover/ svsterr A 2-mcn valve is installed vertically C1 me vapor capping connection and t.-.c 3-mch vaives on tne liquid unicacng cutlets, /.men are over educ tion pices Users may reouce the vapor line vaive to 1 men prov.oing vapor fio.\ is sufficent to maintain positive r"issure near me end of unioaomg, I t liquic c,:;ets _ n ce used to _,,eed unioaomg if .-sired. T-e vaccr oaacmg connection snould be venteo to the vacor at the top of me storage tanx (see unloading q i a g ram), 7>'e mermcwell dome fitt.r g covers a closed system fillec w.tr. antifreeze. A thermometer can oe inserted in tne Unc' epenmg to obtain the tempera ture :f tne vmyi cr.lonae when desired. Vinyl Chloride Monomer Tank Car Dome Fittings 1 G9 rod attambly 2 Liquid unloading valva 3 Vapor padding valva 4 ItQuid unloading valva 5, Safatv raHaf valva 6 TKarmowall 7 Tasting tuba TanK Car *j^icadmq Staton Fof V ^ v C""or.ci^ V . ; % E- i-T.T ' 5 ",g 2tv.ee eer"- :s _s-rrf '"s 'RANGE Full vacuum to SO D$ig GRANGE *50sFto150-F 21 ASI 000013653 Sampling Check contents of tank car by sampling before unloading to verify that con tents of car are vinyl chloride and meet required specifications. Samples are taken in stainless steel pressure bombs that meet the require ments of DOT Regulation 3B-400 and are aeaicated to vinyl chloride service. All pipe connections and valves at the sampling point should be as close togetner as possible to minimize the quantity of vinyl chloride monomer that must be vented before removing the sample bomb from the system. The pipe leading from the sampling bomb is part of a closed loop system. It is connected to a common vent manifold leading to the refrigerated recovery system or to the stack system. If this cannot be done, an alternative is to discharge the vent line no less than 12 feet from the operator, who should have room to stay upwind no matter what tr? .vind direction may be. A suitable Dreathing device must be used during sampling if measure ments of vinyl chloride monomer con centration have indicated tnat expo sure is possible. An alternative arrangement has piping and valves for two evacuated sampling bombs: one for collecting the sample; the otner for collecting me bleed-off. The operator should wear long sleeves and gloves to protect him from possible contact with residual liquid vinyl chloride monomer when he removes the bomb from the sampling position. Liquid samples should oe taken only tnrougn tne gage rod assembly fitting. 1. Remove hood from gage rod assembly. 2. While holding rod. release latch. CAUTIOM: When releasing latch, do not stand directly over roc because tne car vapcr pressure could make the rod rise rapialy once tne latch is released. 3. Set rod to desired level in car. In the center of the other fittings is a sprmg-loaaea. safety relief valve set at 280 psig 000013654 Pressurizing Csr PPG ships tank cars of vinyl chloride filled with liquid up to no more than R6=o of the water weight capacity of -e tank Vmyl chloride vapor occupies a space above the liquid Air or oxygen must not be introduced during unloading or storage to prevent forma tion of a flammaole fixture or prema ture polymerization. Purge all lines thoroughly with, nitrogen before hook ing up Use nitrogen, with a maximum of 10 ppm oxygen. Nitrogen purging can be minimized by sealing the line and alternately pressurizing with nitro gen and bleeding off the nitrogen to a remote location or to a recovery system or incinerator. Remove the threaded pice plugs on the liquid and gas valves cautiously and connect tne liquid unloading line and the vaoor padding line (see un loading diagram), Tne vapor pressure is needed to prime tne centrifugal forwarding Dome, if one is usee To reouce pressure dreo locate tne pump as close tc me tank car as coss'de Some installations ''sve 2 ccmmessor on tn<e uaoo' Ime from me storage tank m ado.tier to me oumo In .".arm climates. 3 ccmoressor ""ay be used a'cne .Mtrcut a camp, tut in cola .\e=mer a ou""c is usually needed-- ..m' cr .wfeut re compressor--*0 ' rate u"i: so np , e vaoor pres- *e ^seo f:r cadd "g sreJo not _ -ceed 225 osm Never ape!, heat tc acce:ert? me unloading of a vinyl cnlcr.oe tars car Tc obtain fiex c lit, m the unloading s.stem. eifer stainless steel hose or steel pme .-. m fiex.ple jomts can be used. T;`e flow cf v.n.l c'lcride from me tank car sr.culc be regulated by a . aive m me ransfer line If the dismarge rate Suddemv ceccmes too great an excess flow creck valve in me tanx car y.ni dose To re-ccen this valve cicse me unioamng ccnnection .awe ur.t'l me pressure $ equalized. Checking Unloading Progress Start unloading by slowly opening the vapor padding connection valve to the car. If it is necessary to dis continue unloading for any reason, close all valves tigntly and disconnect all unloading connections. Tne lines leading from the unloading connection valve and the padding connection valve should be purged with nitrogen so that the vinyl chloride monomer vapor tn those lines is trans ferred to tne recovery system. 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 gage on the unloading line is the best way to indicate when all the liquid has been emptied from the car. 23 ASX 000013655 1 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 bemg 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. Car 90-ton TANK CAR DIMENSIONS Water Capacity 26 000 gal. Length Over Strikers' 50'5" Overall Height2 15'5" Height to Valve Outlet2 14'1 - Extreme Wicth3 10'6V' 'Add 2'7'/2" for i- over center line of coupler knuckles. ^Heights are for empty cars and are measured from top of rail; reignts cf cars may be as much as 4" less. 3Width over grab irons. Note: Height to manway platform is 6" to 10" less than height to center line of valve. Overall Length 487" TANK TRUCK DIMENSIONS Height to Top of Relief Valve 10'8" approx. Overall Wiath 96" Leave at least 10 ps;g cf vinyl chlonce vacor pressure in the empty tank car. ASI 000013656 24 'Unloading tank trucks Tank trucks deliver shipments usually Aitdm a 100-mile radius of Paulsboro. The tank trucks have a net weight ty of 40,000 pounds corresDOndi nominal capacity of 5.200 is. The trucks are unloaded on litner side from the bottom near the back end. Since the sizes of the liquid |,ne connections (3 inches) and vapor padding connections (2 inches) are me 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 different length of pump suction line or vapor padding line would be needed. Users may re duce the vapor padding connection to 1 inch, providing vapor flow is sufficient to maintain positive pressure near end of unloading. Personnel should not sit in the cab a rule unloading, and the unloading should not go unattended. Workers unloaaing smpments snouid wear goggles, protective clothing and pro tective respiratory equipment if needed. me wneels of tne :a Spotting Truck Shut off the truck engine. If for some reason the tractor must be separated from the trailer, do this before making any cc onnections and place a "horse" s strong enougn under tne front ">on't reiy on the support wheels j the load. Set tne brakes and ock the wneels. uocate the vmyl cnloride truck so as to Cr:* it from collision with a passing ve Allow no vehicular traffic in me area until unicacm.g is completed. f tnis cannot Ce cone, ""in:mize and tontrol traffic by temporary roadblocks. In esse of emergency wmle unloaomg, an internal valve can De shut off by nano levers a; tne front ana back of tank truck. . >ms- ,v..; mssfcst . . r ... ASI 000013657 Preventing Ignition Static electricity mufet 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 flangeo Use a commercial meter for checking ground integrity. All wiring and electrical equipment should be explosion-proof. No flameor spark-procucing devices or smoking by 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 Check 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 me 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 `ruck's contents. 'soect the pump, vapor line and liquid ine noses or flexible-joint piping for any defects including leaks. Ground tne tank truck. A fire hcse and hydrant s-culo oe close cy in case of fire. A fire extinguisher should be close at nand. Check storage tan*, teuei oetcre unicao rt to make Sure there is room, fcr :-e t'ucx's cmten Unloading Vinyl Chloride Monomer From Tank Truck ASI 000013658 26 Store the hose or flexible arm off the ground on a suitable support. The CcOoUu|pling covers should be in place to eon out dirt and moisture. 5c hort spool piece at the end of the hV ..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 svstem should be clean, dr. and free of air before monomer is introduced. If nitrogen purging is necessary, it can ce 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 low. Hook up the coupling of the vapor padding line and ground it. Make sure me closure is tignt. If the vapor pressure m the truck drops below 10 psig. deed pressure from the storage-tank i'3DCr space into me truck vapor space Aside from me safety aspects, the storage-tank vapor soace must be practically free of oxygen and other contaminants to avoid incurring cnarges for delaying me truck and purging it after tne truck returns. lf>L.vapor compressor is used m ado o, or instead of. a pump, the essor must not ce capable of ^^eleTlTvvienng over 100 psig. The safety relief valve on the truck is rated at 150 psig. 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. Ik* 7" sf - - W;-.,, 7. ; Hook up the liquic unloaoing line. kt Lever opens and closes internal valve to provide an alternate means of controlling liquid flow from tank truck. Check pressure on emoreo ra-k trut* :c ma*e sure at leas; ? 0 cs c r* u -i i ; v ce vapcr pressure are left. 6SI 000013660 V 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 'iquid valves on the truck and on the lose. Carefully bleed vapor from the r 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 r sures are gone, disconnect the liquid line from the truck and install the blma i coupling covers. Shut off the bleed valve on the liquid line spool piece. 8. Likewise, disconnect the vapor i 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. I i I 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 moaifications 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 equipment to 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 snould be able to withstand working pressures of 1 50 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 t/pe that does not require lubrication. Many lubricants are attacked by vinyl chloriae and snouid not be used. Eccentric-type piug valves are avail able that tignten 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, light and excessive heat. Storage areas should be selected to comply with local codes or authorities. Such organizations as the National Board of Fire Underwriters, 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--ecompression 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. LSi.i.-y. Sorav nozzle for cooling outs.cie ci storage tank in case of fire ;.v/n'* ; ' \ .... - ,r "-- "--v'- v'T v*"-I, , ... c-vys.-si', -.y. y, *!h< . 1 ^ Oine ,s neecea :c cents case a tank s-oslo ruDiure ASI 000013662 30 . Liquid outlet lines to process should ` be equipped with check valves to prevent contamination by backflow. Hequately sized pressure-relief valves / 'd be installed on top of a storage .i, .. To allow for periodic removal and inspection of the valves, they should be installed preferaDly with a 3-way plug cock in the line that can block off first one, then another valve from the tank. Indicators of liquid monomer tempera ture should be installed near the tank bottom to permit observation from the ground. Vapor pressure gages should be connected to the top of the tank out the indicator should be located near the ground. Tanks should also have a liquid level gage with groundievel readout. The level should not exceed 90% of the tank's capacity. Before a tank receives vinyl chloride monomer, the tank should be cleaned and purged with a dry inert gas 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 materials. After a storage tank has been placed in operation, follow standard procedures to prevent oxygen from entering. For example, when tank cars or other 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 to hold up to 50.000 gallons of vinyl chloride; for higher capacities, spheres are preferable. Although vinyl chloride monomer s sometimes stored as a liGuid at at^cspheric pressure by means of remoe'ation, it is usually storea oncer pressure The actual pressure inside a storage tank depends on the ambient tempera ture (see graph on page 10) Forexample. between the freezing pomt cf 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. All vessels in the vinyl chloride monomer system should be mterconnectea c> pressure equalization lines, `which are connected to a refrigerated vaporrecovery system. The term, "vesse's." includes storage tanks, snipping :ortainers and processing equipment. Since it is impossible to condense 100% of the vinyl chloride monomer vapor, the inert gas stream from :he refrigeration unit will contain so^e vinyl chloride monomer. t Reaar.g :31k temoereture me.cater *L Testing storage tanx for oxvger /. :r. a emtable meter a$I 000013663 31 Transfer tines 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 divide into three classes: (1) personal, i 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 tne worker's breathing zone is drawn through a tube that can be cliooed ro his shirt collar. Suction comes from, a battery-operated pump rhar can fir rno his shirt pocket or over his be:t. Acti vated charcoal in the tube traps the vinyl chloride while the pump runs for 15 minutes. For analysis, tne vin.l chloride is removed from the crs-coal with carbon disulfide anc >s sucsequently determined on a labcratorv gas chromatograph having a flame ionization detector An alternative method gaming oooularity because of its speeo 'S an air bag strapped to a worker's cacx A battery-operated pump attacnea tc ms person draws vapor into me tag Injecting a needle into tne bag sets,ns a sample for gas chromatogrspme analysis. 2. Fixed area monitoring uses either a gas chromatograph cr mfrareo spectrophotometer. A sue ~ pu'-'C near the instrument orav nci- through long tubes enc rer fixed-site pickuo points, c. r:rl', ten or twelve points. An automat,c programmer provides segue-mai analyses of the multiple sempimg points for cycles suer as several minutes each. The instrument can ce equipped to sound an alarm .-men a preset exposure limit is exceeded. 3. Portable instruments are used where fixed area monitor.r.g is "O'sctical. They can also serve for cete;: m: leaks and for making rapic sur,e.s m areas. The various tvpes of cc"sc:e instruments used include tne rured spectrophotometer, fia^e .oo.zs: :n instruments, ana instruments mat measure total hydrocarbons &S1 OOO0l3fc64 neiicf wi'vi? .'1 Irjrs'Ji , c ; of Sterile tann 32 :o I.-O 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 the hood. The "sample in" line is connected to a rotameter to measure sample flow. Thus, chromatographic sampling is carried out without removing sample bombs from hood. If the chromatograph has a thermal conductivity detecting cell, the exit gas--consisting of vinyl chloride monomer vapor and the carrier gas-- should be vented to the hood. How ever, if the chromatograph has a flame ionization detecting system, the vinyl chloride will be completely burned to form hydrogen chloride and carbon dioxide. All analyses should De performed wimou! removing sample Pomps from nood. -erscnal mcr.tcr no oev ;e traps any v"r,l c'-iir ae vaocr ;n act .ateo caracal >n tape t_:s a r anc ^rtanle area -':n.:;r no .-strume-t can aiso oe used for detecting ieaxs ASI 000013665 33 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 sraff. Acidity, as HCl 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 hyoroxide. Iron, as Fe This method involves the spectrophotometric measurement of the color produced by the ferrous-p-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 electrometncally utilizing a suitable "dead-stop" titra tion apparatus. Sulfur This method involves the conversion of sulfur m vinyl chloride to sulfate and precipitation as barium sulfate. Barium sulfate is measured turbipimetncally with a spectrophotometer. Acetaldehyde The reaction of carbonyl compounds with 2.4-dinitrophenylhydrazine is me basis of the determination of acetalde hyde in vinyl chloride monomer. The reaction takes place under acid condi tions in carbonyl-free methancl solvent to form the hydrazone, The addition of a solution of potassium hydroxide produces an intense wine-red color. The absorbance maximum occurs at 480 nm ana is measures against a reagent blank. Testing for t-clt : es ,n v-yl chicr de to-.err" wii" gas mrir-atcgtaph at PPG S.ant :r, Lake C-.arles. lc j s ana. AS1 000013666 34 purchasing information Grades PPG Industries produces only polymergrade 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 chloride 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. C rdicated 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 noldmg 5 pounds. The Pittsburgh-based technical service staff of PPG Industries' Cnem.cji Division is available for consulting on handling, storage and use. ASI 000013667 Percarbonate Initiators F r The Polymarizstion Of Vinyl Chloride PPG Industries' Chemical Division supplies a line of peroxyd.carbonate 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 (NPP), di-sec-butyl peroxydicarbonate (SBP) or di-(2ethylhexyl) peroxydicarbonate (EHP). Peroxydicarbonates have the same general formula: 00 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 peroxydicarp^ ates to; Reduce Time of Batch Runs Enable fast rate of conversion du-^R the very first hour of reaction ana, A 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 oowerful oxidizing agents. They are hazardou^^ chemicals shipped under refngerati and must be stored under refngeratii^^f 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 nandle and prefer acamg initiator to process volumetrica'ly instead of by weight. Also. NPP. SBP and EHP are more soluble in most of the solvents used to dilute peroxvcicarbonate initiators More information Detailed information appears m a 40-page booklet. "Percarbonate Polymerization Initiators." form A-961, available on request. ASI 000013668 36 FRIDAY, OCTOBER 4, 1974 WASHINGTON, D.C. Volume 39 Number 194 PART II DEPARTMENT OF LABOR Occupational Safety And Health Administration EXPOSURE TO VINYL CHLORIDE Occupational Safety and Health Standards ASI 00013669 35896 RULES AND RE ULATIONS of the operation or bceause of an acci opportunity to observe the monit dent in the operation, which would mult lng and measuring required by t / In an employee exposure in excess of the paragraph. permissible exposure limit (e> Regulated area. (1) A regulated (8) "OSHA Area Director" means the area shall be established where: Director for the Occupational Safety (1) Vinyl chloride or polyvinyl chloride and Health Administration Area Office Is manufactured, reacted, repackaged having jurisdiction over the geographic stored, handled or used: and area In which the employer's establish (11) Vinyl chloride concentratic- ment is located. In excess of the permissible expo;, (9) "Polyvinyl chloride" means poly limit. vinyl chloride homopolymer or copoly (2) Access to regulated areas shall be mer before such is converted to a fabri limited to authorized persons. A daily cated product roster shall be made of authorized per (10) "Vinyl chloride" means vinyl sons who enter. chloride monomer. (f) Methods of compliance. Employee (c) Permissible exposure limit. (1) No exposures to vinyl chloride shall be con employee may be exposed to vinyl chlo trolled to at or below the permissible ex ride at concentrations greater than 1 ppm posure limit provided in parag-'ch <c> averaged over any 8-hour period, and of this section by engineering. - ac- (2) No employee may be exposed to tice, and personal protective 's S 1910.93*1 Vinyl chloride. vinyl chloride at concentrations greater follows: than 5 ppm averaged over any period not (1) Feasible engineering () Scope and application, (1) This exceeding 15 minutes. practice controls shall lmme section Includes requirements for the (3> No employee may be exposed to used to reduce exposures to a. control of employee exposure to vinyl vinyl chloride by direct contact with the permissible exposure limit. chloride (chloroethene). Chemical Ab liquid vinyl chloride. (2) Wherever feasible engine*, stracts Service Registry No. 75015. <d> Monitoring. (1) A program of work practice controls which ca; This section applies to the manu Initial monitoring and measurement stltuted immediately are not suffi facture. reaction, packaging, repackag shall be undertaken In each establish reduce exposures to at or below : ing, storage, handling or use of vinyl ment to determine If there Is any em mlssible exposure limit, they shall iK.re- chloride or polyvinyl chloride, but does ployee exposed, without regard to the use theless be used to reduce exposures to not apply to the handling or use of fabri of respirators, In excess of the action the lowest practicable level, and shall be cated products made of polyvinyl chlo level. supplemented bv respiratory protection ride. (2) Where a determination conducted In accordance with paragraph Cg) of this (3) This section applies to the trans under paragraph (d)(1) of this section section. A program shall be established portation of vinyl chloride or polyvinyl shows any employee exposures, without and implemented to reduce exposuurens tLoU chloride except to the extent that the Department of Transportation may regard to the use of respirators. In ex cess of the action level, a program for de at or limit, below the permissible or to the greatest extent efxepmi jf regulate the hazards covered by this sec termining exposures for each such em solely by means of engineering and tion. ployee shall be established. Such a pro practice controls, as soon as feasible. <b> Definitions. (1) "Action level" gram; (3) Written plans for such a program means a concentration of vinyl chloride (1) Shall be repeated at least monthly shall be developed and furnished urcn of 0.5 ppm averaged over an 8-hour work where any employee is exposed, with out request for examination and copyir..- day. regard to the use of respirators, 1; authorized representatives of the Ai _ - (2) "Assistant Secretary" means the cess of the permissible exposure Ur tant Secretary and the Director. Sue a Assistant Secretary of Labor for Occupa (11) Shall be repeated not less :__ l plans shall be updated at least ever)' six tional Safety and Health, U.S. Depart quarterly where any employee Is exposed, months. ment of Labor, or his designee. without regard to the use of respirators. (g) Respiratory protection. Where (3) "Authorized person" means any In excess of the action leveL respiratory protection Is required under person specifically authorized by the em (1U) May be discontinued for any em this section: ployer whose duties require him to enter ployee only when at least two consecu (1) The employer shall proride a a regulated area or any person entering tive monitoring determinations, made not respirator which meets the requirements such an area as a designated representa less than 5 working days apart, show ex of this paragraph and shall assure that tive of employees for the purpose of ex posures for that employee at or below the employee uses such respirator, except ercising an opportunity to observe moni the action leveL that until December 31, 1975. wearing cf toring and measuring procedures. (3) Whenever there has been a pro respirators shall be at the discretion of (4) "Director" means the Director, duction, process or control change which each employee for exposures not in ex National Institute for Occupational may result In an Increase In the release cess of 25 ppm. measured over any 15- Safety and Health. U.S. Department of of vinyl chloride, or the employer has minute period- Until December 31, 1975. Health, Education, and Welfare, or his any other reason to suspect that any em each employee who chooses not to wear designee. ployee may be exposed In excess of the an appropriate respirator shall be in (5) "Emergency" means any occur action level, a determination of employee formed at least quarterly of the hazards rence such as, but sot limited to, equip exposure under paragraph (d> (1) of this of vinyl chloride and the purpose - ment failure, or operation of a relief de section shall be performed, use. and limitations of re; vice which Is likely to. or does, result in (4) The method of monitoring and devices. massive release of vinyl chloride. measurement shall have an accuracy (2) Respirators shall be selectee () "Fabricated product" means a (with a confidence level of 95 percent) of among those Jointly approved by product made wholly or partly from not less than plus or minus 50 percent Mining Enforcement and Safety Admin polyvinyl chloride, and which does not from 0.25 through 0.5 ppm, plus or minus istration, Department of the Interior, require further processing at tempera 35 percent from over 0.5 ppm through and the National Institute for Occupa tures, and for times, sufficient to cause 1.0 ppm, and plus or minus 25 percent tional Safety and Health under the pro mass melting of the polyvinyl chloride over 1.0 ppm. (Methods meeting these visions of 30 CFR Part 11. resulting In the release of vinyl chloride. accuracy requirements are available In (3) A respiratory protection I (7)"Hazardous operation" means any operation, procedure, or activity where a release of either vinyl chloride liquid or gas might be expected as a consequence the "NIOSH Manual of Analytical Methods"). (5) Employees or their designated rep resentatives shall be afforded reasonable meeting the requirements of shall be established and malnti (4) Selection of respirators fo. vinyl chloride shall be as follows: ASI 000013670 FEDERAL REGISTER, VOL. 39, NO. 194--FRIOAY, OCTORER 4, 1974 RULES AND REGULATIONS 35897 Atmospheric concentration of vinyl chloride (1) Unknown, or above 3,600 ppm__ <U) Hot ever 3,600 ppn; (111) Hot owr too ppm., (It) Not over 39 ppm. (v) Not over 10 ppm.. Acquired apparatus Open-circuit, eelf-contained breetWn* apparatus, pres- aure demand type, with full /aoepiece. (4) Combination type C supplied air respirator, pres sure demand type, wltn full or half facepiece, and auxiliary self-contained air supply; or (8) Type C, supplied air respirator continuous flow type, wltb full or half faeepleoe. and auxiliary self-contained air supply. (A) Combination type C supplied air respirator de mand type, with full feoepieee, and auxiliary oelf-oontoined air supply; or (B) Open-circuit self-contained breathlnc apparatus with tun facepiece, in demand mods; or (C) Type C supplied air respirator, demand type, with full faeepleoe. (A) A powered air-purlfyinfl respirator with hood, helmet, full or half facepiece, and a canister which provides a semoe life of at least a hours for coscenratlons of vinyl chloride up to 36 ppm. or (B) Oes mask, front- or beck-mounted canister which provides a service life of at least 4 hour* tor concentrstlons of vinyl chloride up to 39 ppm. (A) Comblnetion type C supplied-alr resplretor. de mand type, with half facepiece, and auxiliary self-contained air supply; or (B) Type C supplled-slr respirator, demand type, with hall facepiece; or (O) Any chemical cartridge respirator with an organic vapor cartridge which provides a service life of at least 1 hour for concentrations of vinyl chloride up to 10 ppm. (5) (i) Entry Into unkown concentra '2) Protective garments shall be pro tions or concentrations greater than vided clean and dry for each use. 36.000 ppm (lower explosive limit) may <1> Emergency situations. A written be made only lor purposes of life rescue; operational plan for emergency situa and tions shall be developed for each facility (11) Entry Into concentrations of less storing, handling, or otherwise using than 36,000 ppm, but greater than 3,600 vinyl chloride as a liquid or compressed ppm may be made only for purposes of gas. Appropriate portions of the plan life rescue, firefighting, or securing shall be Implemented in the event of an equipment so as to prevent a greater emergency. The plan shall specifically hazard from release of vinyl chloride. provide that; (6) Where air-purifying respirators (1) Employees engaged in hazardous are used; (1) Air-purifying cannlsters or car tridges shall be replaced prior to the expiration of their service life or the end of the shift In which they are first used, whichever occurs first, and (il) A continuous monitoring and alarm system shall be provided where concentrations of vinyl chloride could reasonably exceed the allowable concen trations for the devices In use. Such sys tem shall be used to alert employees when vinyl chloride concentrations exceed the allowable concentrations for the devices In use. (7) Apparatus prescribed for higher concentrations may be used for any lower concentration. (h) Hazardous operations. (1) Em ployees engaged in hazardous operations, including entry of vessels to clean poly vinyl chloride residue from vessel walls, shall be provided and required to wear and use; (I) Respiratory protection In accord operations or correcting situations of ex isting hazardous releases shall be equipped as required in paragraph (h) of this section; (2) Other employees not so equipped shall evacuate the area and not return until conditions are controlled by the methods required in paragraph (f) of this section and the emergency Is abated. (j) Training. Each employee engaged In vinyl chloride or polyvinyl chloride operations shall be provided training In a program relating to the hazards of vinyl chloride and precautions for Us safe use. (1) The program shall Include; (I) The nature of the health hazard from chronic exposure to vinyl chloride Including specifically the carcinogenic hazard; (II) The specific nature of operations which could result in exposure to vinyl chloride In excess of the permissible limit and necessary protective steps; (11) The purpose for, proper use, and ance with paragraphs (c) and <g> of limitations of respiratory protective this section: and (II) Protective garments to prevent kin contact with liquid vinyl chloride or with polyvinyl chloride residue from vessel walls. The protective garments shall be selected for the operation and devices; (lv) The fire hazard and acute toxic ity of vinyl chloride, and the necessary protective steps; (v) The purpose for and a description Its possible exposure conditions. of the monitoring program; (vi) The purpose for, and a descrip tion of, the medical surveillance program: Irtt) Emergency procedures; (vlll) Specific Information to aid the employee In recognition of conditions which may result In the release of vinyl chloride; and (lx) A review of this standard at the employee's first training and Indoctrina tion program, and annually thereafter. 12) All materials relating to the pro gram shall be provided upon request to the Assistant Secretary and the Director. (k) Medical turveiilance. A program of medical surveillance shall be insti tuted for each employee exposed, with out regard to the use of respirators, to vinyl chloride in excess of the action level. The program shall provide each such employee with an opportunity for examinations and teste In accordance with this paragraph. All medical ex aminations and procedures shall be per formed by or under the supervision of a licensed physician, and shall be provided without cost to the employee. (11 At the time of initial assignment, or upon institution of medical surveil lance; (l) A general physical examination shall be performed, with specific atten tion to detecting enlargement of liver, spleen or kidneys, or dysfunction in these organs, and for abnoRnaltles In skin, connective tissues and the pulmonary system (See Appendix A). (11) A medical history shall be taken, including the following topics: (A) Alcohol intake; (B) Past history of hepatitis; (C) Work history and past exposure to potential hepatotoxic agents, includ ing drugs and chemicals; (D> Past history of blood transfu sions; and (E) Past history of hospitalizations. (ill) A serum specimen shall be ob tained and determinations made of: (A) Total bilirubin; (B) Alkaline phosphatase; (C) Serum glutamic oxalacetlc trans aminase (SOOT); (D) Serum glutamic pyruvic transam inase (SGPT); and (E) Gamma glustamyl transpeptidase. (2) Examinations provided in accord ance with this paragraph shall be per formed at least; (1) Every 6 months for each employee who has been employed In vinyl chlo ride or polyvinyl chloride manufacturing for 10 years or longer; and (ii> Annually for all other employees. (3) Each employee exposed to an emergency shall be afforded appropriate medical surveillance. (4) A statement of each employee's suitability for continued exposure to vinyl chloride Including use of protec tive equipment and respirators, shall be obtained from the examining physician promptly after any examination. A copy of the physician's statement shall be pro vided each employee. (5) If any employee's health would be materially impaired by continued ex posure, such employee shall be with- ttDMAl REGISTH, VOL 39, NO. 194--MIDAY, OCTOSEt 4, 1974 ASI 000013671 35898 RULES AND REGULATIONS drawn from possible contact with vinyl tion which contradicts or detracts from til) The number of employees in chloride. the effect of. any required warning, regulated area during normal operat (6) Laboratory analyses for all bio information or instruction. Including maintenance. logical specimens included in medical (m) Records, (1) All records main (2) Emergencies, and the facta examinations shall be performed in labo tained in accordance with this section talnable at that time, shall be repo ratories licensed under 42 CFR Part 74. shall Include the name and social secu within 24 hours to the OSHA Area'bT (7) If the examining physician deter rity number of each employee where rector. Upon request of the Area Dlrec* mines that alternative medical examina relevant. tor, the employer shall submit additional tions to those required by paragraph (2> Records of required monitoring information in writing relevant to the (It) (1) ol this section will provide at and measuring, medical records, and au nature and extent of employee exposures least equal assurance of detecting med thorized personnel rosters, shall be made and measures taken to prevent future ical conditions pertinent to the exposure and shall be available upon request for emergencies of similar nature. to vinyl chloride, the employer may ac examination and copying to authorized <3) Within 10 working days following cept such alternative examinations as representatives ol the Assistant Secre any monitoring and measuring which meeting the requirements of paragraph tary and the Director. discloses that any employee has been (kKl> of this section, if the employer (i) Monitoring and measuring records exposed, without regard to the use of obtains a statement from the examining physician setting forth the alternative examinations and the rationale for sub stitution. This statement shall be avail shall: (A) State the date of such monitor ing and measuring and the concentra tions determined and Identify the instru respirators in excess of the permissible exposure limit, each such employee shall be notified in writing of the results of able upon request for examination and ments and methods used; the exposure measurement and the steps copying to authorized representatives of (B> Include any additional informa being taken to reduce the exposure to the Assistant Secretary and the Director. <1> Signs and labels, (1) Entrances to regulated areas shall be posted with leg ible signs bearing the legend: C&KCR-Sosracr Agent AMSA AuTHoeiZED Pebsonhxl Oat tion necessary to determine individual employee exposures where such expo sures are determined by means other than individual monitoring of employees; and (C) Be maintained for not less than within the permissible exposure limit. <o) Effective dates. (1) Until Janu ary 1, 1975, the provisions currently set forth In S 1910.930 of this Bart shall apply. (2) Areas containing hazardous oper ations or where an emergency currently exists shall be posted with legible signs bearing the legend: CAWcn-SusracT Agent ik This Asia Florae- 30 years. til) Authorized personnel rosters shall be maintained for not less than 30 years. till) Medical records shall be main tained for the duration of the employ ment of each employee plus 20 years, (2) Effective January 1.1975, the pro visions set forth in } 19l0.93q of this Pan shall apply. Appendix A--Supplementast medical Intoimattoh mm SavtrtcsKT Biomass Actmoauxo PsasoKKn. ONvr (3) Containers of polyvinyl chloride resin waste from reactors or other waste contaminated with vinyl chloride shall be legibly labeled: or 30 years, whichever is longer. (3) In the event that the employer ceases to do business and there is no successor to receive and retain his rec ords for the prescribed period, these rec ords shall be transmitted by registered When requires tests under paragraph (k)(l) of this section show abnormalities, the tests should be repeated as soon as prac ticable, preferably within 3 to 4 weexs. If tests remain abnormal, consideration should be given to withdrawal of the employee from contact with vinyl chloride, while a^^-r Contaminated with Vnm Cimaams Cancex -Sdsfxct agent mail to the Director, and each employee comprehensive examination is made^^&'l Individually notified in writing of this Additional tests which may be transfer. A. For kidney dysfunction: urine exs^Sia- (4) Containers of polyvinyl chloride shall be legibly labeled: Poltvikti, Chloeid* (o Tsade Naks) Contains Vncrt duuoaint Vintl CHscams u a CaHcn-Susncr Agxnt (4) Qnployees or their designated representatives shall be provided access to examine and copy records of required monitoring and measuring. (5) Former employees shall be pro vided access to examine and copy re tlon for albumin, red blood cells, and ex foliative abnormal cells. B. Pulmonary system: Forced vital capac ity, Forced expiratory volume at l second, and chest roentgenogram (posterior-anterior, 14 x 17 Inches). C. Additional serum tests: Lactic acid de (5) Containers of vinyl chloride shall be legibly labeled either: Cl) Vorn CxLoami ErutotT huwins Oas Cnob Faissuas CaKcsa-SOSPacT Agent or Ol) In accordance with 49 CFR Part 173, Subpart H, with the additional quired monitoring and measuring records reflecting their own exposures. (6) Upon written request of any em ployee. a copy of the medical record of that employee shall be furnished to any physician designated by the employee. tU) Reports. (1) Not later than 1 month after the establishment of a reg ulated area, the following information hydrogenase, lactic acid dehydrogenase Isoenzyme, protein determination, and protein electrophoresis. D. For a more comprehensive examination on repeated abnormal serum tests: Hepatitis B antigen, and Uver scanning. (Gees and 8, 84 Stat. 1596. 1599 (29 c 883, 887); Secretary of Labor's Order No 13-71.88 FB 8784) legends: shall be reported to the OSHA Area Di Signed At Washington, D.C., this 1st CaKczs-Sospzcr Agixt applied near the labor or placard. (6) No statement shall appear on or near any required sign, label or instruc rector. Any changes to such information shall be reported within IS days. (i> The address and location of each establishment which has one or more regulated areas; and dAy of October, 1974. John Stender. Assistant Secretory 0/ Labor. (FB DOC.74-23176 Filed 10-1-74:3:84 pm) 000013^72 ASl ICDERAl MGISTn, V L 3f, NO. 1*4--TODAY1, OCT08EI 4, 1*74