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V. V- V t'J REPORT OF SURVETDONE BI MEDICAL ON PLANTS,lfAND 3 'AND THE SALT CAKE - HHEOGEN CHLORIDE PLANT OF ETHIL CHLORIDE . . IABLE QF CONTENTS I GENERAL DESCRIPTION II " DESCRIPTION OF SPECIFIC OPERATION PROCESSES X i* 'it , , * f ... B'Section Tlent.Nbi I:" '?? - Salt'Cake-'HydrogenChloride Plant (Mannheim) 1 AiSeotion Plant No. 3~, { Compressor House.. C:^t6n Plants i and '3 Polymer System `i 1 A/.', * , * *" ' `; HE AI3EABE3TCAL' UBT. OF ACTOAL AND/OR POTENTIAL EXPOSURES IV EEPOSDEES .BT SUES Plant No. i Plant No. 2(Frei) Plant No*. 3 Salt Cake - Hydrogen Chloride Plant (Mannheim) (including Repair Shop of Ethyl Chloride Maintenance) Ethyl Chloride Iteintenance Shops V SIECIFIC EXPOSURES BT CRAFIS/ETHIL CHLORIDE MAINTENANCE . .* " .. i . Crafts and Helpers (Including Bomber of workers in craft) Painters Carpenters Insulators - Outside Machinists Pipefitters Welders ' Electricians Instrument Mechanics Laborers TE ' Work description of each job in crafts Specific job location by craft and approximate percentage of ' total man-hours spent at each location 1 Specific substances encountered on each job and-other -. - miscellaneous exposures - -. - Approximate1 percent of time exposed .l^oeUaneoTb.pertliuBnt^hotes. '> -Ethyl Chloride .parsb'nii&"-.n6ridhg .in T.E.Im area .. ;3fc^"v'i.- AFPEHDiX X.*?"*." ' ' .'s' -:; '* y^' r.** >\;v - '. . . .. ` Paints and tMnnsrs' in' nssvin EEL- and Ethyl Chloride Area: E-058fefc REPORT 'OF SURVEY DONE BY MEDICAL ON HANTS 1 AND 3 AND THE SAIT CAKE - HYDROGEN CHLORIDE PLANT'OF ETHYL CHLORIDE Ethyl chloride is. manufactured here by reacting the basic chemicals, ethylene and hydrogen chloride, in the. presence of a catalyst* The catalyst '- _ > . used in C sections of No. l and No* 3 plant is either anhydrous aluminum chloride dissolved in ethyl chloride or. the metal aluminum. . At No* 2 plant (Prei), however* the ethyl' chloride is produced by reacting vaporized ethyl alcohol and hydrogen chloride in the'presence of zinc chloride. No polymer is formed in this reaction. ^ 1. ">. Raw materials are obtained as follows! Hydrogen chloride produced byt 1* Reaction of Hg and Clg at Section No* 3 Plant. 2* Manufactured at Salt Cake - Hydrogen Chloride plant (Mannheim)* Ethylene! 1. Produced at B section No. 1 Ethyl Chloride plant by cracking a light petroleum fraction, chiefly propane* - 2* Purchased from Standard Oil Company. ' .1, Catalyst! ~ * *' V Purchased in form of anhydrous aluminum chloride or aluminum metal. Hydrogen t - . - Purchased from the Hydro plant of -Baton Rouge, Refinery of Standard Oil. Chlorine! Normally supplied by Sodium Plant by electrolysis of fused sodium chloride* .. . " ' B'-EffiCHON PLANT NO. 1 Ethylene,-CgH^, is obtained by-cracking light petroleum fraction, chiefly propane, by heat and pressure. After clacking the propane, the next step is to take thejaromatic distillates off by low pressure fractionization. These aromatic' distill ates remain liquid-at atmospheric temperature and pressure. The removal of the aromatic hydrocarbons leaves hydrocarbons of and lighter* E-05867 o 0 -2These remaining hydrocarbons are then compressed and farther cracking is done* Refrigerants are used here with different temperatures at different levels* In this process a split is made between ethane and butane; subsequently between ethane and methane, and this process goes on until the last one where there is a split between ethylene (CgH^) and ethane (CgHg). The ethylene then goes to the compressors and is delivered to C section. The butanes and propanes are used in recycling and when stabilized as liquids at atmospheric temperature and pressure are-mixed with the aromatic dis tillates and sent to Standard Oil Company. The hydrocarbons'lighter than ethylene are vented to flare stack and burned* .'-V -SAIT CASE ^IDROGEN CHLORIDE PLANT ' ' (IttHNHEDl) Rydrogen chloride is obtained at Ethyl Chloride by two methods* One process involves the chemical reaction between sodium chloride and sulfuric acid in Mannheim furnaces giving, hydrogen chloride and sodium sulfate (known as salt cake) as the products of this reaction* Sodium chloride is received in railroad cars, is conducted by elevator conveyor and conveyors to three salt storage bins, each with 100 ton capacity. From the storage bins it is again conducted by conveyor system to the salt feed bin, thence to salt weighing scale, thru salt seal conveyor to the furnace* Sulfuric acid, 98J?, is conducted from sulfuric acid storage to constant-feed-tank (overflow back to storage) thence to,acid scale, and thru , / a. iotameter, and then to the furnace*. , ' The furnace is maintained at 1000 at atmospheric pressure by seven gas burners. Within the furnace four opposing arms revolve about a hub. The sodium chloride and sulfuric acid are added at this hub and are kept molten near the hub* Each revolving arm has shoe-like paddles,which constantly force the salt cake to the periphery. When the salt cake forms around the walls and when it is necessary to change the sleeves on furnace arms, a considerable exposure to HC1 is present. At the sides of the furnace there are four outlets and as the salt cake is moved to the periphery it falls thru these openings periodically. It then goes to a macerator, through 2 coolers, thence to elevator and by elevator and conveyor system to salt cake storage E-05868 O' -3building. After it has cooled a bulldozer pushes it thru an opening in the floor into the crusher* < Soda ask (sodium carbonate) is added to the salt cake at this step of the operation to neutralize the excess sulfuric acid irbich may be present i up to 3%. Hie soda ash is added by tub men who break the sack and shake it over the salt cake. She entire operation is exceedingly dusty and as a consequence offers particularly a dermatological hazard since sulfuric acid, salt cake, and soda ash are primary irritants. From the crusher the salt cake is taken by conveyor system and chute to box: cars. It nowrcontains from 0.3 to 1.0^ sulfuric acid. The hydrogen chloride formed in the furnace comes .off as a gas and passes thru a cyclone separator shore the heavy material drops* It then goes, to the cooling tower, to the. cooler-absorber where it is mixed with water forming hydrochloric acid, andthen to the stripper where it is boiled and vaporized. Thereafter it goes to Ho. 3 plant where it passes through a sulfuric acid scrubber after which it joins the common line to plants Nos. 1, 2 and 3. A SECTION NO. 3 PLANT The other process for the production of hydrogen chloride is the combustion reaction of hydrogen and chlorine. The combustion products, con sisting-of hydrogen chloride, air, and snail amounts of -moisture, leave the reaction chamber at an elevated temperature and are cooled, dried and compressed for use in the] ethyl chloride manufacturing' process. The portion of the No. 3 plant where these operations are carried out. is designated as nAn Section. ;Hydrogen is supplied from the Hydro Plant of the Baton Rouge Refinery of the Standard Oil Company of Louisiana where it is produced hy passing methane and steam over a catalyst. The inpurities are principally nitrogen, carbon monoxide, small quantities of unsaturated, low boiling hydrocarbons, carbon dioxide, methane and oxygen.-"The hydrogen stream is metered at 225* psi g. At this pressure the hydrogen is delivered to the reaction chambers (called . .. " ' 'S * .. * *- -- burners) tj^drogm manifoldi- : \r- ,- Chlorine,is normally supplied by- theSodium Plant where it is produced by the electrolysis of fused sodium chloride. The chlorine from the electrolytic cells is scrubbed with water to remove silicon tetrachloride, followed by * pounds pressure E-05869 o -hscrubbing* with sulfuric acid to remove "water vapor and is delivered thru a pipe line to No. 3 plant, "A" Section {at 18 psi g.) where it passes thru a flame trap to the burner manifold. At the northwest corner of the burners chlorine tests are run off the feed line. Pressure here is 20 - 2$ pounds. The chlorine stream from th^electrolytic cells is 9$% pure, the impurities being nitrogen and oxygen.' Ihen the production of. chlorine is greater than the immediate demand the e^ces^is liquified and stored at Sodium Plant -where it is subsequently revaporized as needed. The revaporized chlorine is 100^ pure. TShen Sodium Plant cannot meet the No. 3 Plant requirements, 'the deficiency is met by use of chlorine (1) produced at Solvay Process Company and supplied by pipe line to No. 3 Plant. The formation of hydrogen chloride by the combustion of chlorine in hydrogen is carried out in da Pont type burners. These are lined with refractory brifek to "withstand the high temperature. The metered hydrogen .and chlorine are fed to the 'burners in a hydrogen chlorine m>l feed ratio slightly greater than one to insure Complete conversion of the chlorine and to minimize `the presence of free chlorine in the reactor feed since the presence of free chlorine causes formation of undesirable by products in the reactors. The heat of the reaction is removed by a continuous "water flow over the outer surface of the burner and by radiation. The exact tenperature of the exit gas is not known but has been estimated at 1000 - 1500 P. The impurities are the inert gases in the hydrogen and chlorine feed streams. The burners are sampled for purity every one half hour. , If an excess of chlorine is present there might be a small chlorine exposure although no cases ' have required medical care. The operator`on Section "A" is called a "Burner" or "An Section Operator. He operates the burner, checks area including the cooier side and sulfuric acid drying processes.' He drains knock out drums once each shift and drains off concentrated HC1' solution and at this time a certain amount t of hydrogen chloride comes off giving an exposure. Here too no reportable cases. After leaving the burners the hydrogen chloride is air cooled by passing thru a steel cooling section, a pyrex glass cooling section and a rubber lined flame trap. The gases are cooled to about 100 F. in the steel trombone section by a water drip flowing across the pipes. Although this temperature is below the dew point conposition, very little corrosion takes place because a coating of n<nnn from the chlorine is-formed over the surface of the steel coolers. The gases E--05870 o -S- are further cooled to HO0 F. in pyrex glass double pipe heat exchangers. Each burner is equipped with a cooling section and flame trap so that it can be operated independently of the other burners. The discharge from the flame traps are manifolded and the cool gases delivered to the drying section. If a burner is repaired the gas is cut out of the flame trap into an injector which has a stream of'water running through it causing a partial vacuum and absorbing the HC1* * The greatest chance for exposure isjim the event of equipment failure, particularly if on the chlorine side, % In the drying towers, the'moisture present in the stream is removed by .counter current scrubbing with concentrated sulfuric acid (88 - 98^) in two series operated towers packed with ceramic Raschig rings. The HC1 flowing up the tower is scrubbed by a downward flow of sulfuric acid which lowers the moisture content of the exit gas to less than Q,Q$ wt. % A knock down drum, following the last drying tower, removes entrained sulfuric acid from the dried hydrogen chloride before it is compressed. Die knock down drums are changed about once each shift and a chlorine or hydrogen chloride exposure may occur when the bleeders are opened. The sulfuric acid is changed about once each shift; Then it gets down to 91$. The operator who adjusts the valves wears full acid equipment, (Hood coat, pants and gloves). As pressure is about two pounds, no one has yet been burned by acid who has followed the safety code. The HC1 then goes to the compressors. COMPRESSOR HOUSE Die compressor house is not a part of nAn Section. In the three stage compressor (i.e. compressed', cooled, compressed,cooled, and compressed and cooled) the gas is compressed from'2'psi'g. pounds to 150 psi g. pounds and 100 F. Four -Ihgersole-Rand gas engine compressors are used. (Three in operation while the fourth is serviced.) The EOT that has gone thru the three stage compressor is delivered to \ nC Section ELant No. 3 Another portion of the HC1 from nAn Section undergoes one stage compression and is then delivered to Plant No. 1. E-05871 oo S&. C SECTION PUNTS 1 & 3 The synthesis and purification of ethyl chloride is performed in that portion of Plants 1 and 3 known as "C" Section* The synthesis itself can be reduced to the following operations r (1) Mixing the reactants. (2)' Slinging them In contact in the presence of catalyst. (3) Removing the ethyl chloride produced. .* (1*) 'Maintaining a sufficiency of active catalyst to' sustain efficient conversion. The.reactants (dilute ethylene, concentrated ethylene and hydrogen chloride) are delivered individually to "C" Section but are combined into a mixed feed before being charged'to the, reactors. There.are two reactors in "0" Section, Plant No. 3 and one reactor in "C" Section, Plant No. 1. The reaction between thejathylene and hydrogen chloride takes place in two reaction vessels consisting of steel shells partially filled with a 3 - 1$ aluminum chloride - ethyl chloride reactor solution. The reactors are packed with ceramic Raschig rings to provide contact surface for dissolving the reactants. The anhydrous aluminum chloride is supplied as needed by manually' emptying the drums in which it is received into a mixer known as "cat mixer" which has been blown out with ethylene gas, after being locked. While still closed, it is flushed with an inert gas purchased from Standard Oil and which is probably nitrogen or carbon dioxide. The base plate is then opened and the anhydrous aluminum chloride poured in. Workers doing this are supposed to wear goggles, gloves, body protection and respirators as a potential hazard exists for when anhydrous aluminum chloride comes in contact with moisture it breaks down into hydrochloric acid and aluminum hydroxide, releasing in the reaction an enormous amount of heat, lihen skin or mucous membrane is exposed to this compound, its action is intensely caustic." It is claimed that the substance -sublimates and that the -resultant vapor also causes caustic burns. The reactants, entering through feed distributors, are dissolved in the reactor solution and react fo form ethyl chloride. With a sufficient amount of active catalyst in the solution, the reaction is almost instantaneous. The effectiveness cif the catalyst solution is determined qualitatively from the concentration of unreacted ethylene and hydrogen.chloride in the gases leaving the reactors. A constant temperature is maintained to hold the converter fluid -05872 o -7- level and the rest, all condensable gases and vapors go off overhead. The reaction forming ethyl chloride evolves approximately 610 Btu/lb ethyl chloride and a portion of this heat is used to vaporize the product. The, remainder is removed by heat loss through the reactor shell and by circulation of reactor solution thru water cooled heat exchangers. . Everything but polymer which is a complex aluminum chloride-ethylene compound goes off. Hth normal and efficient operation the reactor overhead gas stream contains from > . <: . 1.5 to 2.5 mole/S hydrogen chloride and 0.0 to 1.5 vole % ethylene. The excess of hydrogen chloride in the reactor overhead gas results from the fact that an excess of hydrogen chloride is maintained in the reactor feed to minimize catalyst consumption polymer formation and isopentane formation. hy-products other than polymer are formed in small amounts during the reaction, during the solution of the catalyst and during the removal of the polymer. The impurities, principally isobutane and isopentane and smaller amounts of related hydrocarbons and chlorinated hydrocarbons, pass overhead together with the/product. The ethyl chloride and heavier materials plus a few light ends are condensed. The remaining non-condensable gases are scrubbed with H2O and caustic and returned to the refinery., The condensed ethyl chloride is put thru a stabilizing tower where light ends are returned to the reactor. The stabilizer bottoms are fed to the re-run still where heavy ends are removed for disposal and ethyl chloride is taken off overhead, condensed and put in product tanks for use. For purposes of reference, a more detailed description rill be found in the subsequent indented paragraphs. - The recovery and separation of the ethyl chloride from the IS reactor overhead vapors is performed in the residual gas. tower system which is composed of reactor gas exchanger, reactor gas precooler, the residual gas tower, the residual gas condenser, and the residual gas tower reflux drum. - The overhead vapors from the reactor at 100 - 125F. are manifolded and partially condensed by cooling, first in the reactor gas exchanger which cools them to 95 F. and second in thepropane cooled reactor gas precooler which cools them to 15 F. At the precooler discharge temperature, most of theethyl chloride in the reactor overhead vapor is condensed. The vapor-liquid discharge from the precooler is separated in the bottom of the residual gas IPSi <C 0I1S hi tcnrer; the' liquid collecting in the bottom portion of the tower and-the vq? or passing tip thetoweri The vapor passing up the tower' (composed chiefly of feed diluents) contains some ethyl chloride not condensed at 1J> F. This is recovered by rectification of the vapors on 8 bubble cap plates and by cooling the vapors leaving the tower to 100 F. in the ethylene, cooled residual gas condenser. The liquid recovered * ' 'V * * in the condenser is separated from'the feed diluents in a reflux drum and is returned to the tower .reflux. The ethyl chloride free vapors from the reflux' drum are used as cooling medium in the reactor gas exchanger and are heated to approximately 95 F. by the reactor overhead gas. These vapors containing the feed diluents plus small amounts of ethylene, hydrogen chloride and chlorinated hydrocarbons are scrubbed with water and caustic and sent to Standard Oil for fuel purposes.- The liquid collected in the bottom of the residual gas tower contains the ethyl chloride product together with impurities, both those less than volatile and those more volatile than ethyl chloride. The impurities more volatile than ethyl chloride are (methane, ethane, ethylene, hydrogen chloride and isobutane) removed by a stripping process in a fractionating tower equipped with feed pimps, a steam heated reboiler, and a water cooled condenser. The ethyl chloride separated from the reactor overhead is pimped from the bottom of the residual gas tower and is charged to the stabilizer thru a nozzle. The low boiling impurities together with some ethyl chloride are vaporized in the steam heated reboiler and are removed from the column as overhead vapors. Thevapors flow to the shell side of a water cooled condenser, part of the ethyl chloride condenses and is returned by gravity flow as reflux to the column. The non-condensed vapors flow from the condenser to the reactors for recovery of their * ethylene, hydrogen chloride and ethyl chloride content. -0 5 8 7 4 The' stabilizer removes ethylene, hydrogen chloride and impurities more volatile than ethyl chloride. 'The ethylene and hydrogen chloride are converted to ethyl chloride in the reactors while the more -9` volatile constituents are eliminated from the system as residual gas. Impurities boiling between hydrogen chloride and ethyl chloride cannot be removed as residual gas due to the low tem perature and high pressure of the residual gas tower condenser. Consequently, the concentration , of such impurities in the system increase until their removal cannot be effected in the - '"J ' ' ' '' , 1 stabilizer .and they appear as product impurities.. Non-condeased .vapors from'the condenser are recycled to the reactor. In order to maintain right concentration of polymer, a certain amount of convertor solution is continuously withdrawn from the reactor and put thru the polymer stills where the ethyl chloride is blanked off and returned to system, and the polymer is removed for disposal. Catalyst destroyed by polymer formation is replenished by adding additional anhydrous aluminum chloride to the ncatn (catalyst) mixer thru which converter solution is then circulated. POEZUER SfSllM Polymer Removal Prom The-Reaction Medium . Polymer, .the high boiling couples of aluminum chloride and ethylene, which, as stated previously, is very much less volatile than ethyl chloride. Consequently, it remains in the reactor solution while the product is removed overhead. The accumulation of this by-product in the catalyst solution results in poor conversion, high catalyst consumption, and low product purity. - To prevent this accumulation, the coupler is removed from the reaction medium by constantly withdrawing a portion of the reactor solution, as described previously, vaporizing the greater part of its ethyl chloride content, condensing the vaporized ethyl chloride for return to the reactors, and discharging the non-*vaporized residue. "The equipment used in this process consists of two flashing stills (a high pressure still and a low pressure still) with their auxiliary preheaters,* condensers, condensate drums and praps. The first polymer still removes (flashes off) the greater portion of the ethyl chloride contained in the reactor solution from the high boiling compounds and the aluminum chloride catalyst. Reactor fluid flows from the 'reactors thru a pre-heater into the still. The stream is metered and flows under the pressure differential existing between the reactors (at 120 psi g.) and the still (at 90 psi g.). At the -first still temperature of 195 F., most of E-05875 vao- :. ~ the ethyl chloride and the -volatile compounds are vaporized (flashed off) and - pass overhead*' TVnn overhead vapor is then cooled and condensed in a -water cooled condenser and is discharged into a condensate drum, the liquid being continuously pumped back to the reactors, i.e., returned to the system.. The bottoms from the first still are fed to the second polymer still which is a low pressure still for recovery of additional ethyl chloride* ,At 12j> F. and 90 -psi g. Of the first still condensate drum, part of the first still overhead is not condensed. This uncondensed portion is exhausted thru ai pressure controller to the lower pressure and temperature (35 psi g. and 20 F.) second still condenser where the ethyl chloride in the stream is condensed together with the.ethyl chloride in the second still over head* -A portion of the low boiling impurities remains uncondensed and is vented from the second still condensate drum to the atmosphere thru a pressure controller carrying -with it a small amount of ethyl chloride* . The second polymer still or low pressure still operates at a lower pressure (35 psi g.) than the first polymer still (90 psi g,) to reduce the ethyl chloride content of the non-volatile residue from the first still to a minimum (3%)* The bottom of the first still flows thru a steam heated pre heater to the second still , where essentially all -the ethyl chloride and other volatile compounds are vaporized at 175 F. This overhead vapor is cooled and condensed in a propane cooled condensor and is discharged into a condensate drum. This liquid from the condensate drum is pumped periodically to the slop tank from which it is later returned to the reactors, ie., returned to the system. The slop tank is used to store impure ethyl chloride. The bottoms of the second still contain a small amount of ethyl chloride, the high boiling complex impurities, and the aluminum chloride catalyst. This conglomerate is called' polymer and is discharged to a storage tank from which it is fed either by pressure or pump to the polymer burner* One 1st class operator and a helper, runs all of n0ft Section and one other man runs samples, analyzes various ethyl chloride, ethylene, ethylene and hydrogen chloride streams for purity. In the analyses the Burrel system is used. Bromine is employed in this procedure, if the reagent bottle containing the Bromine should he broken an exposure to that substance would result. Operators here check levels with bleeders and check the polymer line going to storage. They have possible exposure to polymer and ethyl chloride. '* There is also an exposure to steam in the whole section when the operator a.- -II- checks the steam line* The marker also analyzes reactor overhead and waste gas* . One worker called "Board Man" watches the instruments in the control room and calls the operator* s attention to anything flowing off records data on data sheets. t 4 E-05877 u ALPHABETICAL ZX37 OF ACTUAL AHD/CR POTENTIAL ETPOSOHES .HDland.ETHIL/CBLQHIDE 1EEA . . SPECIFIC SCBSTAHCES ini^jndroua Aluminum Chloride Aromatic hydrocarbons Asbestos Carbon monoxide Catalyst (anhydrous AlClg) Chlorinated hydrocarbons * Chlorine Biamels Ethyl Chloride Ethylene Ethylene Dichloride Karbate Karbate accelerator Lacquer Lead, red Lead fumes (aside) Lead, shite Ifetal fuses Oil, crankcase Oil, penetrating OH, soluble cutting Oxides of nitrogen Tbinnera Turpentine Vareol Zinc fumes (oxide) Zinc chloride C" Fluorides Fluorine Gasoline Grease Havec hydrogen hydrogen chloride Hydrochloric acid Isobutane Isopentane Paints Polymer Polymerisation products * Silicon dioxide Sodium carbonate (Soda ash) Sodium hydroxide ' (Caustic) Sodium sulfate (Salt cake) Sulfuric add See also Appendix I * Complex polymerisation products add possibly coupler chlorinated hydrocarbons, the exact formulae and numbers of Which are not yet known are formed along the lines. Some are definitely irritants and may possibly be toxic and although very improbable, carcinogenic. Electrical burns and shock (From 13,800 volts down to ^00 amps down) MISCELLANEOUS EXPOSURES Heat (Ifcmrihaia) Badiatdon Infra red Ultra violet (Welders) Pneumoconiosis producing dusts - Silicon dioxide (Sandblasters - negligible) Asbestos (Carpenters - negligible) Steam (Ihen testing lines) E-05878 POTENTIAL AMD ACTUAL EXPOSURES * BT SITES* HD1 AND EXHXL f!Hr/tRjnR AEM PLANT MO, 1 Anhydrous aluminum chloride Aromatic hydrocarbons Catalyst Caustic Chlorinated hydrocarbons Ethyl chloride- ' Ethylene Ethylene dichloride Grease hydrocarbons hydrogen chloride hydrochloric acid Isobutane Isopentane Oil Polymer Polymerization products Propane Taxsol PLANT NO. 2 (Frei) Chlorine (from Sodium) Ethyl alcohol, -vaporized Ethyl Chloride Hydrochloric acid Hydrogen chloride Sodium hydroxide Zinc chloride PLANT MO, 3 Anhydrous aluminum chloride Bromine- Catalyst- (anhydrous AICI2) Chlorinate. hydrocarbons Chlorine' Ethyl chloride EthyleneGrease hydrogen hydrochloric acid Hydrogen chloride Isohutane Isopentane Oil Polymer Polymerization products Propane Sulfuric acid 7arsol Steam SALT CAKE-HXDROQEH CHICRIDB PLANT .... . (Mannheim} hydrochloric acid . hydrogen chloride Sodium Chloride Sodium Carbonate (Soda ash) Sodium sulfate (Salt cake) Sulfuric acid Heat REPAIR SHOP Carbon monoxide Gasoline Grease Oil Varsol (?) Bim CHLORIDE MAINTENANCE SHOPS CARPENTER SHOP Asbestos (negligible) Karbate Earbate accelerator Wood dusts VEQXENQ SHOP Acetylene Fluoride salts, volatile Flux hydrogen fluoride Lead oxide (if cut painted metals) Metal fumes Oxides of nitrogen Hash burns" RarHa-Mnn Infra red Ultra violet * Principal exposures, potential or actual. Exposures to substances nw hydrogen inportant only from explosion or:fire standpoint an4 is important actually- as safety problem and net health. E-05879 o SPECIFIC EXPOSURES BT CRAFTS* EOHIL CHLORIDE UAINTEBANCE * ,. .. . . ........... .............................. CRAFT and Average 'Job.Description Number of Employees 1HEBE 1CBK DONE ; SPECIFIC SUBSTANCES ENCOUNTERED (Potential and/or actual exposures) PAINTERS ' * ' PAINTER HEIE&S * ' t Do spray and brush painting* No paint containing lead is sprayed* only brushed Ut 23 / All maintenance helpers, third class* are orig inally assigned as paint er helpers* Thus* the group of painter helpers acts as a pool from which other maintenance crafts draw helpers as needed* Should the helper sheer aptitude in that craft and like the work-he is : Entire B31 ahd Ethyl Chlor ide area : Vhen working at Hannhein, exposures are to those substances in exposure column numbered as follows i 1*. 3* U, $, 6* 7* 8 and 9* and some 2* but very little and for practical purposes may be disregarded* ; 1* Note' list of paints : and thinner* used as : listed in Appendix I* : 2* Chlorine (very little) : 3* hydrochloric acid : h* hydrogen chloride ' $ .Sodium carbonate (Soda ash) 6* Sodium chloride 7* Sodium Sulfate (Salt cake) 8* Sulfuric acid 9* Nhite lead N.B* Approximately 70? of painters and helpers have exposure to the above list about 30? of tine* permanently* PLANT NO* 1 (Approximately 10? man-hours, of exposure.) Anhydrous aluminum chloride Aromatic hydrocarbons Ethylene Ethylene dichloride hydrogen chloride (Boies not constitute much hazard) . Polymer Propane - 4 Conplex polymerization : products along lines* The exact number and formulae of these are ' not yet known* Some are definitely Irritants* - ; PLANT NO* 3 (Approximately ItO? of manhours exposure.) _ Anhydrous aluminum chloride - Chlorine (occasionally a little) . Ethylene hydrochloric acid hydrogen chloride Polymer Propane Complex polymerization products (see next preceding list) Specific exposures by operators are. not gifen in these tables as the substances encounterec by specific operators are adequately-covered'dn the text of this report* THE ONE EXCEPTTOl JSO BUS IS SHOW IN A. SUBSEQUENT TABLE COVERING OEffiiTOBS HtPLCfUiD IN T.E.L. AREA. Their . jobs are not actually Ethyl Chloride but T*B*I* ; E-05880 ETHTL CHLORIDE MAINTENANCE (p.2) CRAFT and Average Job Description Humber of of Craft Employees PAINTERS (Cont'd.) WHERE NOOK DONE Drying'area. Plant No. 3 (10? of exposure time) SPECIFIC SUBSTANCES ENCOUNTERED (Potential and/or actual exposures) Sulfuric acid (When marking in Drying area markers are required to mear full acid equipment PUNT NO. 2 (Frei) ' Chlorine Ethyl alcohol Ethyl chloride Hydrogen chloride (about 30 exposure) Sodium hydroxide (2$f> solution) Sulfuric acid (Have encountered no trouble) Zinc chloride (Solid or liquid, if liquid, is hot.) 2 painters and 2 painter helpers spend All their tine in T.E.L. area on outside Jobe limited to painting tank-cars. Exposure to T.E.L. considered negligible. Painters andhelpers do brush and spray painting in paint. . Shop as necessary. Paint shop is poorly equipped - no exhaust system present. CARPENTERS CARPENTER HELPERS INSULATORS TT INSULATOR HELPERS 8 8 6 '6 NOTES then necessary, ~ carpenters and insulators* are used interchangeably. < *.. ' * Carpenters do carpentry . throughout entire'area . and carpentry and mood marling in carpenter shop; Insulators do neat and frost insulation of cork and asbestos, l.e., insu lation to maintain tempera tures of hot and cold sub stances. They use moulded pipe. Cement is mixed from dry cement. They also sam blocks composed of 8 magnesia and 1$% chalk------- 2 carpenters,.2 Carpenter helpers, 1. insulator, and 1 insulator helper are stationed at UarmTiria full time. The other 6 carpenters, 6' carpenter helpers, $ insula tors, and J insulator helpers -mork at-Plants-1,-2 and 3-as 'needed. They also nork at - Development Section as . needed, Exposures are potential ly the sane as 'those of painters for the same areas. Have potential lead exposure mhen working at Development Section. Carpenter shop. E-05881 Asbestos (Exposure is negligible as far as asbestos is concerned but constitutes a severe nuisance dost doe to no exhaust) ETBZL CHLORIDE MAINTENANCE fp.3) -, CRAFT and' Job Description of Craft Average Number of Employees CARPENTERS (Cont'd.) Two carpenters and two helpers do sandblasting but are alternated as only one machine Is available------------------ IRENE 1DBK LONE All ever area- Cut NARRATE from block form using circular sans* etc* (Have Earbate in pipe, cylinder and block form* Karbala is used to carry HC1 and chlorinated hydro carbons) Carpenter shop Specific substances encountered (Potential and/or actual exposures) -Silicon dioxide (sand) Lead (If part blasted had been painted with lead paint*) -KARBATE (Contains grtphi impregnated under pressu with hinder cement) IShil not a health menace con stitutes severe nuisance dust when saved due to lack of local exhaust. OUTSIDE MACHINISTS n TneTJEKS 15 a? Maintain, grease, and oil machinery, pumps, elevators, conveyors, compressors, etc* as veil as automotive equipment, tractors, etc* 2 mechanics and 2 helpers and one greaser, full time, maintain, grease and'oil praps, elevators, and conveyors at- -- ... .. These workers. In general circulate* Greasers work regularly at Plants 1, 2 and 3 unless needed occasionally elsewhere. 2 machinists and 2 helpers on compres sors (HC1 compressors) 2 greasers and 1 helper work as greasers all over Ethyl Chloride area all the time* 1 machinist and 1 -helper work in salvage, all the time* 1 machinist and 1 helper----work on trucks and tractor* Notes Garage at Mannheim is call Repair' Shops has only natural ventilation Mmnheim --- Remainder of outside machinists not specific ally listed above work all over plant about equally. . Exposures essentially tl> earns as carpenters and . insulators, i*e, plant ' exposures Grease . Oil ' Varsol (Compressors) -- Carbon monoxide Gasoline ' Grease : Oil : Plus exposures at listed immediately belcr, Grease ---Hydrochloric add Hydrogen chloride CHI Sodium carbonate Sodium chloride Sodium sulfate Sulfuric acid Plant exposures wrrmmms AND RIGGERS 23' (Work interchangeably) - - BOTTiKHMAKKR AND BIGGER TtRT.PTgRS ' 23 (Work interchangeably) Over entire area g-05882 Plant exposures; plus exposures encounl in specific jobs such welding, listed below subsequent chart) mm. CHLORIDE MAINTENANCE (p.l) ' CRAFT and Job Description Average of Craft Bomber of Employeea BOILERMAKERS & RIGGERS (Con't.) INHERE WORK LORE SPECIFIC SUBSTANCES RHCOTOTERED (Potential and/or Actual Exposures) Boilermaker* and Riggers and their helpers work inter changeably and do the same work. One day Riggers may be needed and the' next day . Boilermakers may be needed*' Riggers do bracing, pipe-', hanging, stack work, remove . and jTM*an machinery and parts that have to be rigged* Work is more or less the 'same as done by steel construction workers. Also install hand railing and do some welding-- Fabrication is done by boilermakers* Satire HC1 and Ethyl Chloride area - ------ See later chart for exposures of welders NOTE! See also later chart for be Llermaker, helper, and welder w) o go to T.E.L. area. pipefitters.. PTPECTTTTO HBT.FBBS "5T 32 Time fairly equally divided over area' (Outside bulldings) When working at Mann heim Plant exposures plus Graphite and Oil for oiling bolts. ; White load for cementing joints and on gaskets. Excessive heat FIRST CLASS HELPERS SECOND CLASS BEIDERS ~T Over entire HC1 and Ethyl l Chloride area. First class welders do outside welding and weld anything necessary but largely steel and 'stainless steel with occasion ally some brass, bronze and tin. They do both acetylene and electric. When doing acetylene a fits is used. Electric welch ingt use both coated and Tincoated rods. Have welding shop which is open and when coated rods are used local exhaust ic used which is not too satis factory according to the welders. Second class welders do cutting and sometimes cut painted metal but none with lead paint. Plant exposures plus exposures peculiar to welding! Acetylene Flux Fluoride salt, volatile hydrogen fluoride Metal fumes Oxides of nitrogen "Flash burns" Radiation Infra-red Ultra-violet CT.TOTRTP.TA.WS CTTO'pRfP.TtK BUTT-PUSS 10 10 Electricians and helpers do electrical maintenance! Repair, replace, install and inspect electrical equipment such as lights, motors, transformers, fans, vibrators, meters, etc. Cover entire HC1 and Ethyl Chloride area Exposures essentially the same, as those met by painters plus Electrical shock Electrical burns (From 13,800 volts doir to 100 asps, down.) INSTRUMENT -MECHANICS .a . n HKi.pj&g About 20% of manhours spent in -shop. -05883 Exposures essentially th same as painters and to any substance in process ETHEL CKLOHUE MAINTENANCE (p.5) GRAFT and Average Job Description Number of of Craft Employees INSTRUMENT MECHANICS ' a HEIFERS (Cont'd*) Instrument mechanics Install, . repair, replace land inspect all recording, indicating instruments and meters and install, repair, replace and inspect all refrigeration^ units* WhwkE <VQBE DONE About 20JJ man-hours spent' Plant 1*- About IQ? man-hours spent at Plant 2 (ITei) About 30? man-hours spent at Plant .3 About 2Q? man-hours spent at Mannheim LABORERS NOTE: The work done by group classified as laborers is ex tremely diversified and runs all the way from some employed full time in T.E.L, area to a coffee maker who makes and distributes coffee, over entire HC1 and Ethyl Chloride'.area. 10 laborers'-axe assigned to- 3 laborers -work at T.E.L* blender full time HC1 (Mannheim) full time SPECIFIC SUBSTANCES ENCOUNTERED (Potential and/or Actual Exposures) lines* Only about 10? of entire time are exposed to potential hazards. About J>? of entire time spent at Plant 1 are exposed to 2, 3, U & 6, 1* Chlorine - (l? time ir area) 2* Ethylene 3* Ethylene dichloride h* Hydrogen chloride *> Polymer - (10? of time in area) 6* Propane Chlorine (From 6 to 25? of time in area) Ethyl Chloride (Have froi 10 to 15% of time in area potentially ex posed) Hydrogen chloride (Have potential exposure 6 t< 25% time spent in area! Sodium hydroxide (Have nc over 5% time in area w. potential exposure) Zinc chloride (For prac tical purposes con sidered as none) Percent of time spent in area with potential exposures as follows: Chlorine - 20% Ethylene - 10? Hydrogen chloride - 20? Polymer - 10? Propane as refrigerant 1 Sulfuric acid - 5? Percent of time spent in area with potential exposures as follows: Hydrochloric acid and fydrogen chloride - liO? Sulfuric acid - 1;0? Sodium carbonate - none Sodium sulfate - none For exposures see table "Ethyl Chloride personne who work in T.E.L. area" E-05884 EML CHLORIDE MAINTENANCE (p.6) * CRAFT and Job .Description of Craft Avenge Humber of Employees IABORERS (coat'd,). It laborers feed, hopper* and-- add soda aah to salt cake in .salt cake shed VHEBB WORK ioNE Salt cake shed, BC1 (Mnimheia) foil tine- 2 laborers work as clean tip- men in furnace and stripper buildings (1 nan each in 1 tt. 2 furnaces and strippers) 1 laborer acts as porter-- over entire ilanriheiTi area 3laborers work on ground- as general clean up nen -Furnaces and strippersMarmheim, full tine -Mannheim area, full -Mannheim area, full tine- I 1 laborer works at general---- laborer's duties (roustabout) -CP plant, full time- 1 does janitor work in office and shops 1 coffee maker makes coffee- in tool room and makes two daily trips over BC1 and Ethyl Chloride area distributing it -Ethyl chloride area- -Entire BC1 and EthylChloride' area 2 laborers work on 1 truck and- another on another truck as roustabouts and help as necessary. Work pretty much over as general clean up men and haul aluminum chloride to Plants 1 and 3 Entire HC1 and EthylChloride area 2 laborers work in storehouse- as porters or handymen Storehouse- "."specific substances 'ENCOUNTERED (Potential and/or Actual Exposures) Hydrochloric acid Hydrogen chloride Sodium carbonate Sodium sulfate Sulfuric acid See next preceding list -Area sxposures -Area exposures when not in office -Plant Exposures -Plant exposures -Exposures negligible at storehouse 8 laborers work as general yard men for any task as needed over entire Ethyl Chloride area with some particularly specified duties as followsi' Ethyl Chloride area Wash compressors inside and out- - --Compressor houses. Plants- side and add oil as well as keep 1 and 3 building clean when, torn down- dean entire section from'top to- |-C Sections, Plants 1 & bottom, -Dump catalyst (anhydrous aluminum chloride) from drums into catalyst mixer ("cat mix- er") and act as clean 19 man. Polymer spills all the way down ' HLant exposures in genera! plus certain exposures on special jobs' noted beloirt Eras practical atandpoint exposures not significant action and line exposure (See painters) Exposures particularly , tad wet Anhydrous aluminum chloride E--05885 u ETHHi CHLORIDE MAINTENANCE (p.7) CRAFT sad Job Description of Craft Average Number of Employees 1HEHE 1QRK DONE LABORERS (Oont'd.) and must be cleaned up care fully. Clean out activated aluminum Chloride about once every year. General clean up men andclean up around furnaces. Not as much spill here as in Section A. Clean bubble towers 43 Section, Plant No. 1- General dean up men. In---- ----A Section, Plant No. 3* Drying area remove rings--------- -----Drying area, A Section- SPECIFIC SUBSTANCES encountered Actual and/or Potential exposures Hydrogen chloride Polymer . ..-- -Section ex isurea (see carpenters Section exposures. Sulfuric acid (laborers wear full acid equip ment when working in drying area. 1 man acts as general-- clean up man and roust about. Adds Zinc chloride (about a half hour job) three times a-week -* Plant No. 2 (Erei) -Chlorine Ethyl alcohol Ethyl chloride Hydrochloric acid Hydrogen Chloride Sodium hydroxide Zinc Chloride NOTE; Nhen any laborer has worked on a job where he may have had a skin or clothes con tamination by a toxic or dermatitis producing substance he is sent to Change dothes and does not return to work until he has bathed and put on dean dothes. E-05886 APPENDIX I PAINTS AND THINNERS IN USE IN THE HC1 AND ETHYL CHLORIDE 1* Bed lead. No* 7900 (Socony) 2* Bed, No. 310 Fire Equipment, Machine and tool 3* Gray, Primer Surfacer (Da Pont) Undercoat * 2u Gray, Galvanised Iron Primer J>* "White, interior Primer Sealer 6* .Green, Socoiy No* 28G$00 (Interior Bubber Base) ' 7* Green Olive, Brushing Rmael 8* Green Olive, Spraying Lacquer 9* Green Chemical Resistant (Interior Bobber Base) 10* Green Anti Oxide Bronze 11* Green Automotive (Lacquer) 12* Gray Tank Car (Lead-Base) 13* Black Marine Hull Finish (Outside Enamel) lit* Black Heat Resistant (Socony No. 2311) 1$, Black Automotive (Lacquer) 16* Aluminum (Asphalt Base) 17* White Exterior Gloss (Lead Base) 18. White Plat 19*' White Interior SLoss (Enamel) 20* White Lacquer Spraying THTHNEBS 1* Thinner No* 7Tlt Socony 2* Thinner No* 712 Socony 3* Thinner No. 7H Socony, It* Thinner Lacquer * Thinner No* 3717 Duco - Du Pont 6. Thinner Turpentine E-05887 SKETCH NO* Is Layout- of Ethyl Corporation areas Location of bordering companies -05888 E1HTL CHLORIDE PERSONNEL lORKCNO IN T*E*L*i _____ .____ __ JOB AND JOB DESCRIPTION NUMBER ETHIL CHLORIDE MAINTENANCE OUTSIDE MECHANICS ' (Formerly called millwrights) TTET.'PKRP . General tank car repairs and Interior eleaolngt So welding bat do riveting and replace broken parts* Clean lead sludge out of tanks* Clean T.E.L. fluid railroad cars only* Repair' other railroad tank cars* Em ployed in T.E.L. area foil time* $ h. 1 Boilermaker* 1 helper and 1 Welder go to T.E*L* area from Ethyl Chloride to repair tank cars* lime worked in T.E.L. Area quite variable and may be from a few hoars to weeks and may go to T.E.L. area same intervals* ' 3 SPECIFIC SUBSTANCES ENCOUNTERED Potential and/or actual exposures No appreciable exposure to T.E.L* if tank cars have been properly . prepared first. However* if cars have not been adequately prepared* a' marked hazard can be present* See exposures of tank car repairmen in next preceding section this page. ETHIL CHLORIDE OPERATORS (Referred to usually as "BA Operators" i.e.* Bargaining Agency Operators) Hook up. and unhook T.E.L. fluid cars only. Handle all raw materials from tank cars to storage. 3 or U depending on the amount of work." Ethylene Dibromide Ethylene ELchloride Propylene Dichloride Tetra ethyl lead E-05889 --05890 Ethylene Section B Section apray tower Freeh Feed A FURNACE B y Tar and Distillate to storage Jj_______________________________ .^Ethylene to C Section M .H * '* - ?"J\" \ * -f *' \ *. ' W` * .. " * "A*' .&. s'" "B* Ethylene la produced' inM-^fiction "by thermal'cracklng'of a.light petroleum fraction, ehleay^ropane-at B" "0" After cracking the propai&^'the next step .la' the removal oft the . y AROMATIC DISTILLATES. This *accomplished by taking the 'aromatic distillates off by LOW PRESSURE FRACTIONIZATION at C. These distillates remain liquids at atmospheric temperature and pressure. . v . "J* Hydrocarbons of Cjj. and lighter go over. *|! "F" "0" Have split between ETHANE and-BUTANE here. Refrigerant is used here with different temperatures at different levels. ' This process goes on until the iast one where there is a split bet ween Ethylene CgHty and Ethane OgHg Butanes, Propanes, etc., used in' recycling and when .stabilized as liquid at atmospheric temperature and pressure are mixed with aromatic'distillates and sent to Standard Oil. Hydrocarbons lighter than ethylene are vented to flare staok and burned. Hydrogen Chlorine Hydrogen Chloride .. SulfuricAcid . ' A - Acid burners ` Clp & H2 - Chlorine and hydrogen feed lines respectively TT&. T2 - Chlorine and hydrogen flame traps respectively C - Cooler ' E - Ejectors F - Flame traps ~. D - Drying tower i - . . .. KC- Itoock out drums ); k - Knock out. drums i.` . P - HpSOj^ pump . . S - Seal Drum AD - Air drying tower T - Testing equipment for testing . /I-'." o l o -058*92 *'- E--05893 Q(/Y\fL-fc (l (^2ee^>v. E-0S894 4* / s? vy-,, ? ZjEOEND J Ethylene Propane Chlorinated-Aromatic Hydrocarbons V- " '- Hydrogen------ ;---------------------- _ Chlorine------- .......... - ' Hydrogen Chloride Sulfuric Add' .. Polymer ... _...........................-....... ...... ' Sodium Chloride ' ---- Sodium SkjZxSx SulShte n*mw**"' Sodium samaaxx Carbonate --&: Catalyst (Aluminum Chloride, anhydrous) fidinmjtix KxAXftgftxx . ChXBXtXJt POINTS OF EXPOSURE ' '.'feClV' ; 5TV **< >; V > % /v j vSjSO ... f\*' W'sf ' ti% * < ... , t'CMorinp' , -5; - . propane taja# ' *>V;^ . , ethylene' -05895 -Oil--