Document b5R0j5MvBGyV5aJv09oG4wgx1

SHELL CHEMICAL COMPANY A DIVISION Of SHELL OIL COMPANY ONE SHFIL PLAZA P.0 BOX 2463 nous I ON, TEXAS 77001 March 6, 1974' The Firestone Tire & Rubber Company 1200 Firestone Parkway Akron, Ohio 44317 f* L-iT,--\ Attention Mr. W. P. Bray Gentlemen: Attached for your information and use within your company is a copy of the statement presented by Shell at the OSHA hearing on VCM manufacture and use February !5, 1974; During the hearing, expert testimony was given by Dow Chemical Company, and by Professor Os a re Maltoni, Instituto di Qncologia, Bologna, Italy as to the effects observe:! in Sophisticated tests of animals exposed long term to various levels of VCM. B. F. Goodrich testified also as to the discovery of angiosarcoma in livers of certain polyvinyl chloride v/orkers at autopsy. Some follow-up reports on the incidence of angiosarcoma are found in the Wall Street Journal February 19, 1974 page 6, Chemical Engineering News February 25, 1974 ar.d Chemical Week February 27, 1974. We would urge you to make arrangements with the OSHA recorder to receive a copy of the full testimony at the hearing when available. * Enclosed Is a cop}' of our vinyl chloride safety data sheet which we have revised, based ori testimony given at the hearing, to give more explicit warning of the potentialities associated with exposure to VCM. . In this version of the safety data s'^oet, we specifically reference the information from Professor Maltoni that cancer development has been noted in , rats down to VCM exposures of 250 ppm and also the information that exposure to VCM may be implicated in dev^lor-i^^t of liver cancer in some polyvinyl chloride workers. In view of this information, we now rate VCM as a health hazard 3 (using the National Fire Protection Association rating system) and recoim.end air pack or supplied air respirator for personnel protection where such protection is repulsed. We are now preparing for external distribution an expanded description of the sampling :nd a.-iaiyMcal techniques we have been using to determine VCM concentration in workers' breathing zones. When this description is ready, (proiiahiy about iV.rch 15, 1974) we shall send you a copy. As you know, we have adorTod c.\ ..`.orna'i working level of 50 ppm * OCC 017675 2 maximum VCM exposure over eight hours for our operations. We believe that the periodic use^of breathing zone analyses has helped considerably in keeping significantly below this level. Very truly yours, SHELL CHEMICAL COMPANY Attachment f R. J. Reynolds Manager, Vinyl Chloride t * OCC 017676 \ SHELL CHEMICAL STATEMENT TO OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION CONCERNING POSSIBLE HAZARDS OF VINYL CHLORIDE MANUFACTURE AND USE ^ Mr. Chairman: My name is Richard J. Reynolds, Manager Vinyl Chloride, Shell / Chemical Company. I am accompanied here by Mr. Howard L. Kusnetz, Manager ' of Industrial Hygiene, Shell Oil Company and Dr. R. L. Maycock, Manager Environment and Safety, Shell Chemical Company. The Shell Oil Company and its division, the Shell Chemical Company, are pleased to be able to participate in this fact-finding hearing on the possible hazards of vinyl chloride manufacture and use. We are especially appreciative that the U. S. Department of"Labor called this hearing before publishing any proposed regulation. Shell Chemlca'l Company manufactures vinyl chloride mo* nomer (VCfth / at Deer Park, Texas (near Houston) and at Norco, Louisiana (near New Orleans). *c, We entered the vinyl chloride Industry only recently and produce only the monomer. Our remarks will be limited to this segment of the,industry only. Shell's facilities comprise large, continousiy operating process units closely integrated and requiring minimal manual attention or exposure to feed and product streams. Production in the unit at Deer Park, Texas was started in August 1971. Production in the Norco unit was started, in October 1973. Design production capacity is-.about 1,200 tons VCM per day at Deer Park and about 1,000 tons VCM per day at Norco. At Deer Park about twenty persons are involved directly in the day-to-day operation of the VCM unit. Approximately twenty-five adoUional employees are involved less continually with VCM manufacture dining- the regular performance of their, duties in maintenance, shipping and supervision, thus,'at Deer Park, about 45. workers out of a total chemical pla..t staff of 1,300 are concerned with VCM manufacture on a regular basis. At Norco, a similar number of direct VCM workers are required but fewer shipping personnel so about 25 workers of a total chemical plant staff*of about 370 are involved on a regular basis with VCM manufacture. The principal raw materials used in our VCM production units are ethylene and chlorine. At both Houston and Norco the ethylene is receive^ by OCC 017677 c- 2- - pipeline. Chlorine at Houston is received by pipeline and at Norco by railroad tank car. Small quantities of dichloroethane are received at both locations by barge to supplement these primary feeds. At Houston small supplemental quantities of hydrogen chloride feed are received via pipeline and tank truck. The process technology employed at both Shell VCM units was licensed from Stauffer Chemical Company. In this process, about half of the ethylene and all of the chlorine fed are reacted to form the main intermediate which is 1,2-dichloroethane. After purification, the 1,2-dichloroethane Is heated in a furnace to form product VCM and the main byproduct, hydrogen chloride. The product VCM is purified to greater ihan 99-.9% purity by distillation and stored as a liquid under its own vapor pressure. The byproduct hydrogen chloride is recovered by reaction with the remaining half, of the ethylene feed and with air to form additional 1,2-dichloroethane. Minor byproducts of the process include: carbon oxides, chloroform, carbon tetrachloride, ethyl chloride, the isomeric dlchloroethylenes, the isomeric trichloroethylenes and trichloroethanes, tetrachloroethanes, and the isomeric chlorinated butanes. The process is a continuous one. The reactants, intermediates, byproducts and product VCM are contained'within the process equipment in a closed system except for a continuous stream of waste process nitrogen which is vented from a high stack after water scrubbing. Occasionally there may be minor vents such as from loading arm drainage or leaks. The process equipment ; cner.td on1:/ m:.intnr:rc.-, :,:i then only after 'washing followed by frring of retd, prodttti or byproducts contents. Mai nt or a nee. operations are generally infrequent (maintenance shutdowns are scheduled only -once or twice a year), The general precautions for containing and purging organic materials in large chemical process equipment are well known to us as a result of our long history of manufacture and handling of flammable materials and chlorinated compounds. When the process technology was licensed, a substantial compilation of toxicological information on VCM and associated feed and byproduct compounds was received from the Jifcensor. Also we had available considerable other toxicologic information dealing with compounds already handled.by Shell Chemical OCC 017678 4 -3- such as chlorine, ethylene and ethyl chloride. This information is available to the public in toxicologic reference works; therefore, we will avoid requoting it here. Initial review of the VCM process toxicology information available to us in 1969 and 1970 led us to conclude that additional studies of our own were not required. Thereafter, in a paper delivered at the 1970 International Congress on Cancer by Viola etal, ^ it was reported that tumor development was observed in rats exposed repeatedly to high concentrations of VCM. The exposure levels in the Viola work (30,000 ppm) were grossly In excess of published standards. Nevertheless, the report raised a new concern as to what hitherto unknown effects might be' expected with exposure to lower levels. TJius, we accepted an invitation by the Manufacturing Chemists Association to participate with others in the industry in sponsoring an exposure study to elucidate the possible effects of VCM at much lower levels and ^participate in an epidemiology study. These programs were described __>in detail to you by the Manufacturing Chemists Association today. Shell Chemical has provided financial support and has participated actively In these programs from the outset. From the time our Deer Park unit began VCM production in August of 1971 until early 1973, periodic spot measurements were made of the ambient plant air in the operating unit using standard colormetric VCM detector tubes. All measurements were well below the 0SHA 500 ppm*ceiling level and the 200 ppm time weighted average Threshold Limit Value set by the ACGIH in June 1972. Fro>m*"l . V* C'/.l orionce ith other vcV.tila and flammable materials, we ware that the plant ambient air contained loss than 2C0 ppm VCM fcut*this could not be verified because the detector tubes are not sensitive to much lov:er values. It was apparent that a new analytical method would be required to measure low levels of VCM and also that improved sampling techniques would be required to compensate for the greater effect of variances introduced by weather conditions and sampling'location at low levels. Therefore* a sensitive gas-chromatographic analytical technique for VCM in air was developed and (1) P. L. Viola, A. Bigotti and A. Caputo, Cancer Research, Vol. 31 p. 516 (1971) OCC 017679 l -4- sampling was modified to meet, the needs of the situation. A copy of the method is appended. # Based on a developing concern and with the new analytical tools, our company elected to establish an internal worldng level of 50 ppm (eight hour time weighted average) maximum exposure to VCM concentrations in air. This level and the possible implications and incentives for minimizing exposure indicated by the Viola work.ware discussed with our employees in July-August 1973. On August 15, 1973 we formally advised all of our customers of our new working level and the reasons for it (copy appended). Along with the new sensitive analytic technique we had our workers periodically wear an improved device for taking a continuous sample over eight,hours of the air in worker's breathing zone. Results with the improved sampling and measurement technique showed no values iri either VCM plant location exceeding the 50 ppm VCM eight hour time weighted average. Special tests were also made to ascertain the maximum VCM exposure a worker might receive under abnormal conditions : at the jeb site. Under some of these conditions, we found values of .100 ppm - 200 ppm VCM but these concentrations persisted only for a short time. m Based on these tests, additional piecenHons and directions were put into practice. In 1973 we began a program of medical surveillance of VCM workers who would be regularly assigned to jobs involving potential or regular exposure to VCM. Twenty-five workers at Norco werejjiven the examination described below. Forty-tv;a examinations will have been given at Deer Park when the current examination cycle is complete. The annual examination provides for: (!) Mniical hi story (?) physical by a physician (3) laboratory Mood studios including R!?C, hematocrit, . hemoglobin, WBC, differential count, and platelet count (4) SMA-12 blood chemistry including serum bilirubin (5) Routine urine examination (6) 14 X 17 I'-a Hiest X-ray a Based on existing knowledge, with the veiy low accumulated exposure of our workers to VCM we would not expect these examinations to provide any data beyond that establishing a baseline fot subsequent medical history. In fact, to date. OCC 017680 i 5we have found no liver damage or cancer among the Shell participants. Although we have not been#onstream long enough to have meaningful epidemiological data of our own, Shell Chemical is a financial supporter of the Manufacturing Chemists Association epidemiology study contracted to Tabershaw Cooper Associates and described to you today. In addition to the above actions, we continue efforts to locate and curtail emissions, should they be-found, throughout our process units and associated loading areas. With respect to Item 6 in the notice of this hearing, Shell Chemical would favor the route of the regular rulemaking under Section 6(b) of the Occupational Safety and Health Act for a VCM standard, as opposed to an t Emergency Temporary Standard. The rulemaking procedure would allow the * orderly development of data. i? OCC 017681 ' V `jlflLL OIL COMPANY' ' ** SHELL CHEMICAL COMPANY SHELL DEVELOPMENT COMPANY SHELL PIPE LINE CORPORATION i - RATtHO* MATERIAL SAFETY DATA SHEET Information on tnia form it furnlthwf totaiy tor th* ourpota o* compiianea with tna Occupational Safaty and Maaith Act O* 1*fO and than not Oa utad for any otnar ourpota. Uta Or dittammation of all or any part of thu information for any otnar ourpota may raauit in a notation o law onan ttituta groundi for laeal action. SECTION 1 MANUFACTURER'S NAME . ,_ Shell Chemical Company ADDRESS (Number, Stmt. City, Stott, ond ZIP Codtl p q 3qX 2463, A Houston, EMERGENCY TELEPHONE NO. (713) 473-9461 Texas 77001 Chemical name and stnonvms Vinvl ChloTide. Chloroethvlerie^Chloroethene CHEMCAL FAMILY Vinyl Halide FORMULA trade name _____ Vinvl Chloride Monomer fVCMI SECTION II HAZARDOUS INGREDIENTS* COMPOSITION Vinyl Chloride 100 "Extended exposure or rats to Known concentrations' of VCM vapor ranging from 30,000-250 ppm has resulted in cancers of a variety of organs, including a rare cancer of .the liver. No cancers or other effects have been reported in animal exposed to 50 ppm. After years of exposure to unreported concentrations of VCM and other chemicals asso ciated with PVC production, some workers have developed degeneration of the ends of the finger bones. A larger than normal percentage have shown some degree of liver abnor mality. A few have developed the same rare form of liver cancer found in the rat studies. Where the-human exposure levels are known (160 ppm average over 17 years), na clinical illness or overt condition attributable to VCM was found. Some blood test values appeared to be altered, however. Detailed reports of the" toxicological studies are available for examination in the Plant Safety Office. In view of the above, VCM must be accorded the precautions appropriate for a cancer-suspect agent. ^. SECTION III PHYSICAL OATA ' COlLlr. G =0. T 1 -'1 VAPon b VAPOR DENSITY <AIR = t> .Solubility :n water * appearance andooor olfactory fatigue hazardous levels. A ^ OCOO TXT * ^ 7 2580 2.15 SPECIFIC GRAVITY |H;0 = 1I PERCENT VOLATILE BY VOLUME ' ' evaporation rate ( =1) 0 0.cl * Slight . uoxoriess, sweet, smell:Lng gas. Odor tnresnoiu sdouc zau ppm, Dut occurs, so odor cannot bei relied upon to provide warning of { SECTION IV FIRE AND EXPLOSION HAZARD DATA Flash point IMtthed u*ad) -108 F., T.O.C. FLAMMABLE LIMITS _______ Ll at ordinary temperature 3.6 EXTINGUISHING MEDIA CO2, dry chemicals special fiae fighting PROCEDURES d0 not use water exCept as a spray or fog. u.i 33.0 Wear self contained breathing apparatus. UNUSUAL FIRC AN0 CXNLOSJON mAIANDS Handle as an extremely flammable liquid and eas. is under pressure* * Modified by Sjit/f 0*/ Company OCC 017682 Material MSDS-645-4 SECTION V HEALTH HAZARD DATA fHwwotd uwr mm 0SHA_ 500 ppm (celling); ACGXH - 200 ppm (TWA); Shell - 50 ppm (IWA) crrccTt or ovtutxcosuni hee~Section II Also, exposure to very high concentrations may cause asphyxiation, persistent irregular heartbeat, unc nsciouSness, nausea, or dizziness. Liquid on body or clothing may cause freezing or lead to above symptoms via overex- --posure from inhalation-or-systemic absorption. Remove4*3 F.RST AID RROCOuRt.J J victim to arrea free of vinyl chloride vapors. Give artificial respiration if necessary. Remove contaminated clothing ' " ` Notify, supervisor immediately of spills Remove from eyes with large amounts of water, or leaks. STABILITY UNSTABLE SECTION VI REACTIVITY DATA CONDITIONS TO AVO'O X Avoid sunlieht and/nr hpat* and emliufo all oxvcen incompatibility STASiC fo ovoid) . air, oxygen HAIAR03JS 0EC0MF0S T ON PRODUCTS H Cl, CO and phosgene on combustion hazardous POLYMERl ZATION t MAY OCCUA WILL NOT OCCUR CONDITIONS TO AVOlO X air, sunlight and/or heat ww * '- SECTION VII SPILL OR LEAK PROCEDURES T*M Tu Ht .i Ar[h lr.1 A U*UIA| 15 RI.I MD 0* SRlI LlO _ - -r_ FLAMMABLE. *Remove all sources or ignition. Remove all ventilation from cxplosion-oroof equipment. Allow to evaporate -slowly. naste Disposal mlthoo ,,Do not" permit matertia,l to enter sewers. ,U* se controlled, evaporation* Guard against fire and explosion hazards. - SECTION VIII SPECIAL PROTECTION. INFORMATION REERIRaTORT PROTECTION (SpmClfy *ypt) A..ir pac,k or supp,li.ed, a.ir respira^tor as. required- . ^ 'C A' "* *'5 Fi-r:hly recommended (Use enolosion nroof eouiument') | MECHANiCAI (Otnttoll OTHER i KUDDer To oreventOTHER PROTECTIVE EQUIPMENT _ ^ ** all * contact . t ! t - w , - - , wM |Chemical zoeeles and/or w.ith. ,body' as r- equired. face shields SECTION IX SPECIAL PRECAUTIONS reojt.ons td be t*<en in h*noi.i4 *nj storins prevent any leakage. Provide sufficient ventilation to prevent high concentrations. Keep away from all sources of ienltion. an extremely flammable material which is stored under pressure. AVOID BREATHING VAPOR Handle as D. M. Sheets, Supervisor Regulatory Affairs - Chemical Products Shell Chemical Company________________ _______________________ ttM f Fal.pwl-y ]97/| TH( I<iF3 Am Af OS COSTA KID MC4CI*! * BASC} 0 DATA CONR'SKHtP AC* C.RATC- nOftCVC* hO ^AARALTr 19 (J|P*|ftCD 0* <MPLlC9 RtttAROiN- Th ( AC Cu RAC T OP Tn(aR DATA OR THE *CULT* TO IE OfTAINCB MOM TNC UC ThIAiOR. vtSOQA At.iuc NO roil INJURY to VtMDtt ON THINO PCNsOnS PROl.MAtCCT C*UtO RV Till MATERIAL If RfAAONAilC lA'CTv PROCtOuAt* AR( NOT AOmCACO *0 A1 RTiPuLAfCD IN tit DATA AHtlT AO0iTlCiNAt.LT. AIIUMII NO RCAOONRIOILM'T tOR f*JO*T TO VCnOAC ON ThiAO RCRaONB PROSlMATlLf CAuAtb AT Ull Uf ThI M4 UAlAt <N i* | IAMU PNt*CIDuftl AR< YUlt-OWtH ttm>n litt AA A All A Afc i*# IHI MAIA`R OCC 017683