Document oqmz0ZN8DV5G7QwOLa8LxK1g

PROCESS FOR THE PRODUCTION OF AROCLORS, PYRANOLS, ETC. AT THE ANNISTON AND AT THE K. 0. ETOJHRICH PLANT April 1955 ............................- S. Mather Distribution. List (aaended July 19, 1956) 1. Hr. J. S. Brough, London 2. &r. N. B. Dyson, Newport 4 Newport T.I.2. file 3. Mr. 0. V.'Taylor, Newport 4. Mr. Q. V. Taylor, Newport * Newport Process Superintendent 5. Mr. V. 2. Baser, Ruabon 6. Mr. J. F. Sticldey, St. Louis * Krumarlch Plant 7. Mr. J. F. Sticldey, St. Louis *> St. Louis Library 8. MCL file at St. Louis 9. Mr. D. B. Hosaer, Anniston 10. Spare held in M.C.L. file at St. Louis 11. Dr. V. A. Hayward's file Ruabon also Section IX, Specifications and Test Methods, to Newport Analytical Department. |0o^i Co ^ STLCOPCB4023899 VI. PROCESS IN DETAIL, contd. Packing Procea Detail The finished Aroclcrs are run off into drums, a piecs of d< cloth being tied on the pipe outlet for the lighter'Aroclors^anc 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 materia are being filled'directly from the delivery of the filter. Newpo arrangements for filling and weighing drums are discussed in Lond Engineering Pinal Report, September 1951, page 108 and 1 F3-10, also in the start-up reports, July 24, and September 27, 1951. The drums must be clear, and dry, especial care being needed with electrical grades. Newport complaint NP/61, November 1951, of turbidity in 12^8 was traced to the presence of water in the drum* 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 al The gaskets for the bungs of the drums have to be correctly choser A sample of the gaskets supplied by the Meiratn Supply & Gasket Cc to the Krummrich plant was sent to MCL, April 1947. See also the x.discussion -oiLgaakeda-.Gjy-pagaL-2^ --Seeeion* 4STy^be-l-owv - -' *r"^ 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 i. Section VII,'comments, page 17 below. Generally speaking, the distilled Aroclors are packed in galvanized drums, the undistilled ones in black steel drums. Plaked 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 ir steel vessels sprayed with tin or zir.c, or aluminbm lined. AOm 0C2c Ennnorr? 47 STLCOPCB4023900 c )< VI. PROCESS IN DETAIL, coned. vi - Free Deta Packing, contd. Since the Aroclors are such effective solvents , they damage ar are damaged by. ordinary paints, lacquers, insulating varnishes. This feature is Important in connection with hydraulic fluids * containing Aroclors. See, for example, MCL Research Prcr-ess re 1151, DP 5V26/T an* DP 5V277/6 and 1152 DP 4/ic/7 and 8* July 1 etc., also the Section III, Physical & Chemical data, above. Dr for electrical grades cf Aroclors are not painted. Newport Plant Technical Committee meeting, April 14, 1953, page 1 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 t the drums. Aroclors also are dispatched in rail car3. At the Krummrich plan the manhole of the car is protected by a tarpaulin tent during fi Newport plant report for July 195^ mentions the installation of tank-filling facilities. The Krummrich plant operating instructs August 10, 1954 mention that rail cars for Pyranols and Aroclors are insulated and have either a steam coil or a steam Jacket. Th< are lined with Aluminium or else sprayed with tin and zinc. Only dry air la used for unloading. MCC have a "Christmas Tree" fittir a one piece fitting carrying air valve, dip pipe, release valve^_ , andsJiCSsaure_-gaug-r'i-for->ua'-onrai'l' tanks-.* ^Tt^-drs- imp'oiddant'To-'Sra the coll cr Jacket of the rail tank in cold weather. Galvanized or lacquered drums are used for Pyrantls. K0000^8 ACM 0C2`. 48 STLCOPCB4023901 XI. HAZARDS 1 Toxicity XI - Kazar . There are many literature referenees*to harmful effe--3 0r t*. tof "ehlor acne" resulting from exposure to chlorlna*^ "-'e-*il' especially m cases where people working with small e'ec'-'Mi c- ponents have been exposed to the fumes of hot, highiy"chic-<nate' Aroclors. Chlor acne Is sometimes acccmjxaed by gastr^ *troub'es" and there are literature references to liver troubles'. '* ' There was some trouble of this land 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 dipher. 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 tine 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 1 The "Chemist Analyst", September 19^7, Volume 36, No.2 page 32 ..31>-aada -reporX-'-^by_^r-^M;=-'0. - .Last# rv-AnniaSo^ piant, -1937.' -gi-v on the toxicity of diphenyl. MCC Bulletin P-ll5/ientionst0?^to 1.0 mg. per cbm ir. air ae th highest safe concentration of higher Aroclors, and 10 ng. ter more-highly chlorinated Aroclors. H. B. Edkins "Chemistry of Industrial Toxicology", page .-9 giv 0.5 to 1.0 mg. as the allowable limit in working rooms. The MCC Bulletin "Physical Properties of Aroclors" mentions sys temic effects arising from the oral injection of Aroclors. See the letters, B. Mather to P.J.C.Haywood, December 17, 1551. Mather to Newman, January 8, 1952, reviewing the literature on toxicity of Aroclors. See also correspondence relating to the article in Chem. & Hhg. May 17, 195^, pages 2038 and the warning labels menti^ed on page VT-3^ above. AGP CO STLCOPCB4023902 XI HAZARDS, contd St. Louis, Main Office Mr. P. J. C. Haywood Newport (Airmail) n ^ , Mr. W. H. Dr. H. R. Mr. S. M. Dr. D. S. Mr. ?. T. Decerr.be r 11, 1951 AROCLORS: :TOXICITV Since writing to you on December 3rd I have come across a letter of nine to Mr. W. M. Cooper, London, June 24, 19*8, (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. Sartre'3 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". F000040 "cm 5q E. Matr.er STLCOPCB4023903 n - HAZARDS, contd. XI Ha 2 a The Chemist Analyst, Vol. 36, No. 2, page 33 J. T. Baker Chemical Co., Phillip3burg, n. J*. September 19^7 * ON THZ TOXICITY OP THZ "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 32.5^ U9^6) ), has reconsaended the substitution of one of the "Arocblors" as the melting-point bath liquid in preference to th 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. Por 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 Wltlng-polnt 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 handle 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 Knnno4ipossible consequences be presented together with reconnendations fc correct handling. STLCOPCB4023904 XI HAZARDS, contd. xr Kaz Kr. A. C. V. Pennington of Newport, reporting on hi3 Ane-- can tour, December 29, 1950, page 5 writes: * "HEALTH AND SAFETY": "At -Anniston, no special protective clothing i3 provided the Diphenyl and Aroclors operators. A dally change of cloth! was provided In the past but this practice ceased before the w Gauntlet leather gloves and face shields are, of course, avail as required on the plant. " Tins of cold cream ointment, theatrical quality, are t< in the building, but the application of the cream is left to tl operators decision of the Job in question. The men are expect) take a bath, in their own time, at the end of the shift. A go< quality soap, and alcohol for rubbing down purposes, are provie The operators are sufficiently trained in the need for persona: cleanliness that a record of bath taking is not warranted. "Eaergency showers are provided on each floor of the Dipt, 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 se 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 se: 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 hand and face should be washed well before eating. "Baployees in torSc departments are given an annual r.edica examination and a lung X-ray every three years.". F,000(M2 52 0 STLCOPCB4023905 XI. HAZARDS, ccnti. x: - Kazar Toxicity, contd. A good deal pressure of of work has been done on the Aroclors, and on the deteminar icn determinat ion of tj..e of/'con vap u: er.tra: of Aroclors in air. See pages 9- Section III, above, fc a sur of this work. In 1950 (letter April 20, N. P. Rapps to E. Mather) the Ad.rd.ralt 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. Eller.burg, March 15, 195^ mentions work done by H. B. Richa: Jr., of MCC, June 17, 1953. on the determination of the concentr: 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 in." A question has been asked about the possible harm to plants if Ar containing paints are used in greenhouses. The reply is that mos paints are somewhat harmful, and there is no evidence that Arcclc: make then worse. Aroclors have been used as rabbit repeilants, w: 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 note above a concentration of about 3 mg per cbm in air. Newport plant report for December 1951 records bums by hoc Aroclor -- a ease of a splash into a man's eye -- without serious damage. Packages of Aroclors leaving the Krummrich plant tear a label call attention to possible toxic_effects. 1:0000S3 CT A c ^ CCt STLCOPCB4023906 3Q. HAZARDS, contd. Fire Hazards Diphenyl, of course, will bum, and reasonable care i3 rveede* in handling it. Precautions with toluene are mentioned also on oa-- VI-29, and under "Special Risks", below. * The Aroclors are handled as if non-inflammable. Drams of rater4, are melted in the middle of the operating building, by open gas" flames, and open gas flames are freely used to heat pipelines. An instruction, dated April 28, 19^8, calls for a daily inspectic 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 traru formers containing Aroclors, but this is not thought to be a majo-j risk. Safety Equipment Each operator in the Krummrich Aroclor plant is supplied with gogg rubber covered gloves, canvas gloves, rubber shoes and fume respir See also page XI-1. A spare suit of clothes is kept in a case in .d^p.^jp^i;v..-wThs_'.'Uie!pa.rtant.^jasthi*usuai - '-aid --cab i ne tV^'gaS-'S: (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. QSphenyl might start to bum in chlorine gas if conditions in the ehlorinator were badly out of line. A Davis "Vapotester", model M-l,. Type A, (Division of Davis Emergen Equipment Co., Inc., Newark, N.J.) is held in the department for us in testing the air of the working building after toluene has been used, and for testing vessels before men are permitted to enter, an before "flame certificates" are given. The instrument contains a F,000044 ' ACM CO 2 54 STLCOPCB4023907 XI. HA2AJJ3, contd. XI - 7 Hazard . Special Risks, contd. catalytic cell electrically heated to a fixed tempera fare, and th air to be tested is aspirated through it by means of a "squeeze ball". If combustible vapours are present, the temperature of th 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. Plame 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 ua< 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. Benigr.ua, of St. Louis, September 1953, discussed the dangers of using Aroclors in indoor paints. He discounted the possible dangers from phosgene formed by flash dischargee in transformers charged with Aroclors. - See the references to safe handling of glycidyl phenyl ether on pages IX-161 etc. a AC* 0C2` 55 STLCOPCB4023908