Document 7O8J6zyM1Jxd46yw8k6DJ16Ba

K r V / < copy ko. PROCESS FOR THE PRODUCTION OP AROCLORS, PYRANOLS, ETC. AT THE ANNISTON AND AT THE WM. 0. ERD59CRICH PLANT April 1955 -- -- ------- E. Rather Distribution List (amended July 19 1956) 1. Mr. J. S. Brough, London 2. Dr. N. B. Dyson, Newport 4 Newport T.I.E. file 3. Mr. 0. V . `Taylor, Newport 4. Mr. 0. V. Taylor, Newport <* Newport Process Superintendent 5. Mr. W. E. Hamer, Ruabon 6. Mr. J. P. Sticldey, St. Louis * Krummrich Plant 7. Mr. J. P. Stickley, St. Louis 4 St. Louis Library 8. HCL file at St. Louis 9. Mr. D. B. Hosmer, Anniston 10. Spare held lnM.C.L. file at St. Louis 11. Dr. W. A. Hayward's file Ruabon also Section IX, Specifications and Test Methods, to Newport Analytical Department. cc VI. PROCESS IN DETAIL, contd. VI - 34 Process Detail Packing The finished Aroclcrs are run off into drums, a piece of diaper cloth being tied on the pipe outlet for the lighter Aroclor3 , and a piece of fine gauze for the heavier Aroclcrs, which have to be handled hot. This, of course, is to arrest stray bits of pipe scale etc., but the precaution is now omitted at the Krummrich plant when material: are being filled' directly from the delivery of the filter. Newpor arrangements for filling and weighing drums are discussed in Londoi Engineering Pinal Report, September 1951> page 1D8 and 1 F3-10, also in the start-up reports, July 24, and September 27, 1951. The drums must be clean and dry, especial care being needed with electrical grades. Newport complaint NP/61, November 1951, of turbidity in 1248 was traced to the presence of water in the drums. Apparently, in presence of water, the Aroclor reacted on the galvanizing of the drum. Newport plant report, December 1951 mentions the installation of equipment for drying the drums. Care is taken not to do any packing if there is HC1 fume in the air The gaskets for the bungs of the drums have to be correctly chosen. A sample of the gaskets supplied by the Mfiirath Supply it Gasket Co. to the Krummrich plant was sent to MCL, April 19^7. See also the u^^-^ftcUfSsian .flaskets^on-page.-2j*r-Seet-ion' -3S->>^be-l-ow'v Mr. Pemberton, December 1950, collected samples cf the labels used at -the Krummrich plant; cne a patent list label, and the other a warning label on toxicity. The effect of exposure of Aroclors to metal contact is discussed in Section VII.,'comments, page 17 below. Generally speaking, the distilled Aroclors are packed in galvanized drums, the undi3tllled ones in black steel'drums. Flaked or milled solids were packed in barrels or Leverpac containers, bulk solid or resinous Aroclors go out in friction type lid drums, (galvanized for the distilled grades). Storage and blending of the distilled Aroclors is done in steel vessels sprayed with tin or zinc, or alumintm lined. AOM 0 02 5 3c 47 c( VI. PROCESS IN DETAIL, contd. vi - 3 Proces Detail Packing, contd. Since the Aroclors are such effective solvents , they damage, and are damaged by, ordinary paints, lacquers, insulating varnishes, e This feature is important in connection with hydraulic fluids containing Aroclors. See, for example, MCL Research Progress repo 1151, DP 54/26/7 and DP 54/277/6 and 1152 DP 4/16/7 and 8 July 195 etc., also the Section III, Physical & Chemical data, above. Drum, for electrical grades cf Aroclors are not painted. Newport Plant Technical Committee meeting, April 14, 1953, page 2, reported some promising tests with lacquered drums for electrical grades. It was decided not to use lacquered drums for resinous Aroclors on a returnable basis, because the lacquer suffered at the high temperatures likely to be used in melting the material frc the drums. Aroclors also are dispatched in rail csr3. At the Krummrich plant the manhole of the car is protected by a tarpaulin tent during fill Newport plant report for July 1954 mentions the installation of tank-filling facilities. The Krummrich plant operating instruction August 10, 1954 mention that rail cars for Pyranols and Aroclors are insulated and have either a steam coll or a steam Jacket. They are lined with Aluminium or else sprayed with tin and zinc. Only dry air is used for unloading. MCC have a "Christmas Tree" fitting, a one piece fitting carrying air valve, dip pipe, release valve ,...a n 4 s J3 (5 S .a s u r e - -a u g e -^ 5f !o r -'iU fl:e ^ o n k r a l* l- t a n k s * .* ^ T -r *d .'s - 'i m p t f r i a h t ^ ' t'o 1' " c fr a ir the coil or Jacket of the rail tank in cold weather. Galvanized or lacquered drums are used for Pyranols. ACM 0 C 2 5 3 48 r K XI. HAZARDS. xi - Has a: Toxicity There are many literature references*to harmful effects of the r of "chlor acne" resulting from exposure to chlorinated diphenyls' especially in cases where people working with small electrical cc ponents have been exposed to the fumes of hot, highly chlorinatec Aroclors. Chlor acne is sometimes accompanied by gastric troubles, and there are literature references to liver troubles. There was some trouble of this kind among the production workers Anniston in the early days of the development of the Aroclors. A that time highly chlorinated Aroclors were being made from diphen which had come from low grade benzene. Since good benzene has be used, the same Aroclors have been made without trouble. In March it was reported that the Anniston diphenyl and Aroclor plants had 12 years without lost time accident. Prom the start of Aroclor manufacture at the Krummrich plant the operators have been supplied a clean change of clothes every day, and time has been allowed at the end of the shift for bathing. Operators are advised to wash hands and face before eating. The Anniston operators do not have the same issue of clean clothes. * Percy May, "Chemistry of Synthetic Drugs" , 3rd edition, page 2 The "Chemist Analyst", September 19^7, Volume 3, No.2 page J>; S'* on the toxicity of diphenyl. _ .(new edition) MCC Bulletin P-llP/mentions O o to 1.0 mg. per cbm in air as th highest safe -concentration of higher Aroclors, and 10 ng. i'cr more-highly chlorinated Aroclors. H. B. Edkins "Chemistry of Industrial Toxicology", page l-*9 giv 0.5 to 1.0 mg. as the allowable limit in working rooms. The MCC Bulletin "Physical Properties of Aroclors" mentions sys temlc effects arising from the oral injection of Aroclors. See the letters, E. Mather to P.J.C.Haywood. December 17, 1951 Mather to Newman, January 8, 1952, reviewing the literature on toxicity of Aroclors. See also correspondence relating to the article in Chen. & S~.g. May 17, 195^ pages 2038 and the warning labels mentioned on page V I -3^ above. A> C02532 49 c XI. HAZARDS, contd. XI Haza: St. Louis, Main Office Mr. P. J. C. Haywood Newport (Airmail) cc: Mr. W. E. Hamer, Ruabon Mr. W. H. Ritchie, Ruab Dr. H. R. Newman, Ruabo Mr. S. M. Kulifay, Krum Dr. D. S. Weddell, St. , Mr. F. T. Marshall, St. December 11, 1951 A R O C L O R S : :T O XICITY Since writing to you on December 3rd I have come across a letter of mine to Mr. W. M. Cooper, London, June 24, 1948, (copies to W.D.S., W.H.G., and others), calling attention to an article in the J. T. Baker Company's "Chemist Analyst", Volume 26, No. 2, page 33, September 19^7. I attach a copy of this article, and I think you will agree that the warning relates only to really bad exposure, not such as should occur in ordinary analytical work. On October 27, 19^7 Mr. Barbre of the Krummrich plant sent a copy- of the Journal to Dr. Jenkins at Anniston for comment. Dr. Jenkins did not make any comments at the time, but the following extract from Mr. Barbre's letter is inter esting: "During the 11 years of production here only one man evidenced dermatitis. He had also shown similar symptoms in several other departments. When making Aroclor #1270 which is flaked, a noticeable amount of fine fume solidifies in the air. If men are exposed to it during hot humid weather, the skin is irritated, but we have not had any difficulty in curing cases of dermatitis from It". ACM 50 E. Mather oc c XI - HAZARDS, contd. c XI Kaza. The Chemist Analyst, Vol. 36, No. 2, page 33, J. T. Baker Chemical Co., Philllpsburg, n . J. % September 19^7 ON THE TOXICITY OP THE "AROCHLORS" (sic) Robert M. Brown, Chief Industrial Hygiene Section, Division of Health Dept, of Public Welfare, City of St .Louis,-Mo. A recently published article (Maglio, M. Martin, Chemist Analyst, 33 9^- (19^6) ), has recommended the substitution of one of the "Arochlors" as the melting-point bath liquid in preference to the customary sulphuric acid. As stated in that article "Arochlors" are a group of chlorinated diphenyls produced by the Monsanto Chemical Company. There is need therefore to give warning. For the toxicity of these compounds has been repeatedly demonstrated, both from the standpoints of their absorption from the Inspired air, as well as from their effects in produ c.lng a serious and disfiguring dermatitis when allowed to remain in contact with the skin. Since these effects have been repeatedly observed, industrial hygienists have taken care to see that the proper controls have been established wherever these products are used. Por example, the maximum allowable concentration of chlorinated diphenyl for an 8-hour working day is 1 milligram per cubic meter of air. It is probable that nothing like an uncontrolled industrial expo sure will occur -in the laboratory. However, whether an individual is subjected to a possible acute exposure to chlorinated diphenyl, and its serious consequences, will depend upon the size of the melting-point bath, the caution with which it is used, and the temperature to which it may be heated. Likewise, with careless handling of the material and the resulting contamination of the skin, clothing, laboratory towels, work table surfaces, etc. the way is left open for the producing of dermatitis. Scrupulous cleanliness must be Insisted upon wherever this material is handled X The foregoing remarks have been prompted by the belief that in re commending the use of a material with which is associated a potent!; hazard from the health standpoint, it is very important that the possible consequences be presented together with recommendations fo: correct handling. 51 ACM 0C2 c XI HAZARDS, contd. <r XI Kaza: Mr. A. C. W. Pennington of Newport, reporting on his American tour, December 29, 1950, page 5, writes: "HEALTH AND SAFETY": "At Anniston, no special protective clothing is provided the Diphenyl and Aroclors operators. A daily change of clothing was provided in the past but this practice ceased before the wa: Gauntlet leather gloves and face shields are, of course, availat as required on the plant. " Tins of cold cream ointment, theatrical quality, are to in the building, but the application of the cream is left to the operators decision of the Job in question. The men are expected take a bath, in their own time, at the end of the shift. A good quality soap, and alcohol for rubbing down purposes, are provide The operators are sufficiently trained in the need for personal cleanliness that a record of bath taking is not warranted. "Emergency showers are provided on each floor of the Diphe: building and safety notices are widely used. "At St. Louis, Plant B, the Aroclors building is rated a toxic department. Each operator is provided with a complete set of clothing comprising hat, coat, trousers, combination under clothes, socks and rubber shoes. A clean change of clothing, except shoes, is placed in the operator's locker in time for the following shift. Men working extra shifts are given a clean set of clothing. Canvas gloves and goggles are provided and 'Ply' hand barrier cream is available for use when necessary. "Twenty minutes' paid time is allotted for bathing at the end of the shift but, again, no record is kept that baths are actually taken. Theoretically, food is not allowed to be eaten within the Aroclors building. Instructions are issued that hand3 and face should be washed well before eating. "Employees in to::ic departments are given an annual medical examination and a lung X-ray every three years.". ACH oc; 52 r V ' yv o^ X I . HAZARDS, contd. XI - : Hazard Toxicity, contd. A good deal of work has been done on determination of the vapour pressure of the Aroclors, and on the determination of/concentrate of Aroclors In air. See pages 9-, Section III, above, for a sumr of this work. In 1950 (letter April 20, N. P. Rapps to E. Mather) the Admiralty expressed interest in the determination of micro-quantities of Aroclors. MCC have a method for the determination of traces in air by means of the "Halidometer". Mr. Ellenburg, March 15 1951* mentions work done by H. B. Richar Jr., of MCC, June 17 1953 on the determination of the concentra of Aroclors in air. Mr. Ellenburg also states: "-- ----work on the safe limits of Aroclor vapour concen tration in air is being carried on by the Medical Department at the Kettering Laboratories in Cincinnati. This work on animals is well under way, and will help us to know a little better Just what is the safe limit of Aroclor Vapours that one might work i n ." A question has been asked about the possible harm to plants if Arc containing paints are used in greenhouses. The reply is that most paints are somewhat harmful, and there is no evidence that Aroclor make them worse. Aroclors have been used as rabbit repeliants, wi out doing any harm to vegetation. Care is needed in laboratories etc. where Aroclors are used in heating baths; there should be very positive ventilation. The vapours of hot Aroclors are distinctly irritating to eyes and nose above a concentration of about 5 mg per cbm in air. Newport plant report for December 1951 records burr.3 by hot Aroclor -- a case of a splash into a man's eye -- without serious damage. Packages of Aroclor3 leaving the Krumnrich plant tear a label call! attention to possible toxic effects. 53 'ACM CC2 cc XI. HAZARDSy contd. XI Haza: Pire Hazards Diphenyl, of course, will burn, and reasonable care is needed in handling it. Precautions with toluene are mentioned also on page VI-29, and under "Special Risks", below. The Aroclors are handled as if non-inflammable. Drums of rateria: are melted in the middle of the operating building, by open gas flames, and open gas flames are freely used to heat pipe lines. An instruction, dated April 28, 19^8, calls for a dally inspection of safety showers, fire extinguishers and gas masks, a check list being provided. Flanged Joints on Aroclor heating system can be a source of fume. See the notes on gaskets, page 2, Section XII, below. Phosgene may be generated in electrical flashes and fires in trans formers containing Aroclors, but this is not thought to be a major risk. Safety Equipment Each operator in the Krummrlch Aroclor plant is supplied with goggl rubber covered gloves, canvas gloves, rubber shoes and fume respira See also page XI-1. A spare suit of clothes is kept in a case in t ^_...5dp.^rt^^t..-^.T^-.-jdep.ar-fia*n&.-5has->'the:---usuai ^fd-rst^-aid-cabinet,^'ga^TSS (chlorine), fire extinguisher, (toluene, diphenyl), stretcher, safe showers, drinking fountain, eye bath. Special Risks The usual care is necessary in dealing with chlorine, in lighting the gas furnaces, and in handling hot materials, steam lines etc. Diphenyl might start to b u m in chlorine gas if conditions in the chlorinator were badly out of line. A Davis "Vapotester", model M-l,. Type A, (Division of Davis Emerge.nc Equipment Co., Inc., Newark, N.J.) is held in the department for use in testing the air of the working building after toluene has been used, and for testing vessels before men are permitted to enter, and before "flame certificates" are given. The instrument contains a ACM C02 54 cc XI. HAZARDS, contd. XI - 7 Hazards Special Risks, contd. catalytic cell electrically heated to a fixed temperature# and the air to be tested Is aspirated through It by means of a "squeeze ball". If combustible vapours are present# the temperature of the cell rises, and the Indicating thermocouple registers on a cali brated scale. The Instrument has a zero adjustment, and It Is checked twice a month by the Instrument department. Flame certificates must give the number of the Vapotester used# also the data of its last cali bration by the instrument department. The instrument has been use ful in detecting gas escapes, and in tracing spills of gasoline, etc.# from a neighbouring oil refinery Into a public sewer which runs under Monsanto territory. Mr. Benignus, of St. Louis, September 1953 discussed the dangers of using Aroclors in indoor paints. He discounted the possible dangers from phosgene formed by flash discharges In transformers charged with Aroclors. See the references to safe handling of glycidyl phenyl ether on pages IX-l6l etc. A k A C f* C C 2 55 c V J JI S*" - * / > t )#*- /+*/<. ct,i Sm-cS / 9jTT ~ *j*t^ -- * +* ~25 *"TV- 56 AOM 0 0 2 5 3 9