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ETHYL CORPORATION INTER-OFFICE To Messrs. A. J. Baefner, F. C. Holmes, C. E. Major Address From R. L. Johnson Subject Monsanto Technical Service Bulletin Address Date 7 September 18,1964 Attached or each o you is a copy o a recent Monsanto Technical Service Bulletin on vinyl chloride monomer. The section on Storage Life, page 2, is quite interesting. RLJ:gr Attachment R. L.Johnson ETHYL. CORF. CRAB SEP 211964 1 WEF FEW PC. FLH CWM AOW ---- Hg FILES SFC FWF JOJ KLL JRX DEJ RLM CRB " AFL DOH SNH r.*S fC 4-403 VINYL CHLORIDE MONOMER ' ' pCRAGE AND HANDLING INTRODUCTION at ordinary storage temperature necessitates spe VINYL CHLORIDE MONOMER contains an cial provisions for either storage under pressure or aliphatic double bond which permits it to poly- . refrigeration. Refrigerated storage is not consid rr.crize, copolymerize and undergo other chemical ered practical due to continuing operation and reactions. It is used chiedy in homopolymerizution by the suspension and emulsion polymerization techniques. It should be noted, however, that com mercial production of its copolymers is becoming quite significant, as is its use as a chemical inter mediate to a lesser extent. I: a few simple precautions are observed. Vinyl Chloride Monomer can be used, stored, arid han dled safely in both large and small quantities. Monsanto is a major producer of Vinyl Chloride Monomer, and our experience in storing and han dling this material for the past several years is out i lined briefly here. Monsanto will gladly pro vide technical assistance to customers in installing stor age and handling facilities for Vinyl Chloride Monomer. maintenance cost and due to the risk involved if the refrigeration system should fail. The most common types of pressure tanks are long horizontal cylindrical tanks and spherical tanks. Spherical tanks are believed to bo more economical for large tanks since less weight of steel is required to contain a given volume of material. Tanks should be of carbon steel plate and of all-welded construction. Cost evaluations should be run in each individual case to determine if spherical or cylindrical tanks would be more economical and also to determine the optimum size tanks to be installed. Tanks and equipment should have a designed working pressure of from 100 to 150 psi and pro visions should be made for either a water spray sys cm to cool surfaces of tanks, or a suitable in MATERIALS Cr CONSTRUCTION Steel is a completely satisfactory material for handling of Vinyl Chloride Monomer. Copper or ccpper-benring alloys should never be in contact with aimer the liquid or vapor of Vinyl Chloride Monomer as it might result in the formation of explosive acetylides from acetylene which is a trace impurity in Vinyl Chloride Monomiir. sulation such as foam glass to cover tanks. We strongly recommend a water spray system on the tank in any case to cool its urfaces in case of fire to nrevent heat builduD. Liquid 11 lines for tanks may enter at the bot tom of tanks, or they may enter at the top. In the latter case, they should extend to the bottom in order to prevent accumulation of static electricity while ailing tanks. Liquid outlet lines may eater tanks at cither the top, bottom or sides of storage 7r** r A TAN ICS tanks, but it is recommended that they be so axed Underwriters regulations cite: speci as to take material of: at a point about six inches fy certain features which affect actual installation above the bottom of the tank. They should also be of storage tanks. They should be consulted before provided with check valves to prevent contamina the design of storage facilities has been completed. tion of tank contents by backflow from the process The vapor pressure of Vinyl Chloride Monomer lines. ' '_ . **.. A. t V MONSANTO CHEMICAL COMPANY Hydrocarbons Division St. Louis, Mo. i [Monsanto LIZJ pQ A 4-0 A All tanks and rilling equipment should ho "rounded to orevent saarking. Tanks should be provided with temperature in dicators near the bottom to enable observation of the liquid temperature. Pressure gages should he connected to the top of the tanks to measure vapor pressure within. The gages should be located at ground level to eliminate the need for climbing to the too of the tanks for taking readings. Properly sized relief valves should be provided on the tops of tanks to provide.for relief of exces sive pressure. Monsanto's practice is to install on each tank two duplicate valves, each of which would allow for relief of the entire contents of the tank in case of are. These are installed so that each may be blocked off from the tank by plug cock to allow for periodic removal and inspection of valves. If desired, rupture discs may also be placed between the tank and valves. Liquid level gages should be employed and liquid level should not exceed 90% of the total capacity of a tank. Concrete or earth dikes of sufficient size to con* tain the contents of a tank should be constructed to contain any spillage that might result. Local or Underwriters regulations should he consulted concerning this and other safety aspects of storage facilities before installation of the facilities is begun. New tanks should be free of all scale, dirt, grease, water or other foreign matter before re ceiving Vinyl Chloride Monomer. Before being nut into service a tank should be purged with inert gas until free of air. Monsanto will gladly recom mend cleaning procedures for new tanks or tanks converted from other use so as to insure that the cuaiity of Vinyl Chloride Monomer remains good Piping Black steel nine, ASTM A-53 has been found suitable for handling Vinyl Chloride Monomer. Fittings and connections for iyfi" and larger pipe should be hanged or butt welded. Fittings and connections tor 1 ann smal.er may ^.e .breeder: and 3es;-C-Life No. 270 Joint Compound (I. H. Craneoli Cb., Los Angeles, California) or equiva lent used. Centrifugal, positive displacement and gear type cast steel pumps arc satisfactory for Vinyl Chloride Monomer service. Mechanical seals are r ended for use with them. Valves Standard steel gate and globe valves arc satis- factory for Vinyl Chloride Monomer service. 31ue African asbestos is suitable packing for valves. Lubricated steel plugcocks are satisfactory in Vinyl Chloride Monomer lines and may he de signed to use: Nordstrom 755 or P-55 lubricants ." Stick or pressure lubricants or equivalent. Gaskefs Garlock No. 7021,1/16" thick asbestos gaskets, ' or equivalent, arc satisfactory for hanged connec tions. Teflon, Velumoid, lead and carbon are also suitable. V* Filters It is recommended that a filter be inserted be- tween storage tanks and processing equipment A cartridge type filter with fine or medium re' placeablc cartridge is suggested. This can be a: Stayr.ew ELS-7B (Dellinger Coip., Rochester, New York) Fulfiow WXFDS-10-2 (Commercial Filter Corp. Boston, Mass, or equivalent Filter cartridges should be inspected and* re newed periodically.' insulation Tanks should be insulated with 2 to 4 inches of foamed glass brick, or equivalent, unless th,oy are provided with water spray systems to cool surfaces of tanks. A suitable covering fpr insulation to pro tect it from the weather is: Insulmatic No. 410 Asbestocite or eauivalent. * STG.UAGa Ll.-E Vinyl Chloride Monomer is considered a stable , monomer for storage purposes so long as it remains in contact with metallic iron. It is nor mally sold, shipped and stored in mild steel pressure vessels, and may be stored for periods of several months without change in quality in such containers. In vessels lined with glass or other materials which would prevent contact of Vinyl Chloride Monomer with metallic iron, poly merization may be expected to begin in 4S hours, Such polymerization in non-ferrous storage con- 4405 tair.crs can be prevented by the addition to the Vinyl Chloride Monomer of phenol inhibitors in the range of 40-100 parts per million. It is neces sary to remove the inhibitors before it can be used in polymerization reactions. 570"AGS IN CYLINDERS Vinyl Chloride Monomer in cylinders of 5, IS and . 200 pound capacities are available from Monsanto. These should be stored in an upright position out side buildings in an isolated, well ventilated area which is protected from the sun's rays. Cylinders should be secured to, prevent their falling over,. and valves and safety devices should be protected tram accumulation of grease, dirt, water, ice, snow or other foreign matter. All other safety precau tions for storing and handling flammable, liquified gases in cylinders should be adhered to. LOADING AND UNLOADING TANK CASS/ TANK "SUCKS/ AND CYLINDERS There are several satisfactory methods tor un- ' ` loading tank cars and tank trucks of Vinyl Chlo ride Monomer. The user should consider tho meth od he thinks most convenient and economical in view of his own particular situation. Vinyl Chloride Monomer tank cars may be un loaded by applying inert gas pressure to the gas inlet lines. This forces liquid out the liquid outlet line of the car and into the storage tank. Cylinder nitrogen may be used for this purpose. A variation of this is to pump Vinyl Chloride gas from the gas line on the storage tank into the gas line of the car. The difference in pressures effected by this opera tion will cause the Sow of liouid from the c;m to A the tank. It should be pointed out that care must be taken not to exert pressure within the car in excess of its rated working pressure. Another method of unloading tank cars is to connect a line from the gas line of the car to the "as line of the storage tank to maintain equal vapor pressures between the two vessels. Liquid mono mer can then be pumped from the carrier to the storage tank. This nrccedure can also be used without the vapor equalization line; however, care must be taken that heat and pressure in the storage tank do not become excessive. Vinyl Chloride Monomer tank cars should al ways be left with a positive pressure inside :hem after unloading. Air must never be allowed to enter these tank cars, and the cars must never have heat applied to them to accelerate unloading, Tho same provisions for unloading tank cars apply to the unloading of tank trucks. Vinyl Chloride Monomer cylinders may be dis charged by placing them in a water bath which . is at a temperature of 50aC. (122F.) to increase vapor pressure. Heat should not be applied to cylinders by other means. Air should never be allowed to enter cylinders, and they should always be returned with positive pressure in them. Users should not attempt to refill cylinders. More detailed instructions for the unloading of tank cars containing flammable liquids is con-' tained in MCA Manual Sheet TC-4 and in ICC regulations. Sec. 74-560 to 74-563 inclusive. Monsanto will also assist in any technical problems concerning unloading of Vinyl Chloride Monomer.. SAFETY PRECAUTIONS Vinyl Chloride Monomer has explosive limits of 4 to 22% by volume in air and a flash point of *--10S.4aF. (open cup). It is classified by the In terstate Commerce Commission as a flammable liquified gas. In general, all precautions for the storage of flammable liquified gases should be observed for Vinyl Chloride Monomer. Vinyl Chloride Monomer has a sweet character istic odor; however, its irritating effect may not be sufficient to warn of the presence of dangerous concentrations. It is generally recommended that concentrations for an eight-hour work day not ex ceed 500 parts per million by volume in air. In cases where concentration of vapors may be ex cessive, only persons with approved respiratory equipment should be allowed to enter. Vinyl Chloride Monomer cylinders may be heat ed by means of a 50 *C. (122 F.) water bath to facilitate discharge of monomer by its vapor pres sure; however, heat should not be applied by any other means. Heat s'nouk. never be applied by any means to a Vinyl Chloride Monomer tank car or storage tank. Air should never be allowed to enter cylinders, tank cars or storage tanks. Cylinders and tank cars should always be left with a positive pressure after unloading. All equipment handling Vinyl Chloride Mono mer at normal temoeratures should have a de- i. signed working pressure of 100--150 psi. Any system which may be closed at anytime with Vinyl 'Chloride Monomer in it should have duplicate relief valves installed. All equipment should be of steel, and no copper or copper-bearing alloys 0 4A06 should be allowed to contact Vinyl Chloride Monomer either in its liquid or vapor form as highly explosive copper acetylidcs may be formed." All cylinders, tank cars, nil lines, storage tanks, etc. handling Vinyl Chloride Monomer should be grounded. Vinyl Chloride Monomer should be handled in well ventilated areas removed from dangers of open dames, heaters, sparks, and other sources of ignition. In carrying out operations around stor age facilities, only explosion-proof motors and non-sparking tools should be used Buildings 1rous ing processing facilities should He completely ex plosion-proof. Fire-fighting equipment should he available to persons working in those are:is. Car bon dioxide and dry chemical extinguisher; arc suitable. Vinyl Chloride Monomer itself is not absorbed by the skin; however, the phenol inhibitor is ab sorbed by the skin and may cause severe skin irritation and bums if portions of the skin exposed to the liquid monomer are not hushed profusely with water. Protective equipment, including face goggles, should be worn where handing may re sult in spillage. Clothing or. bandages contami nated with the liquid monomer should be immedi ately removed to prevent freezing of the skin or frostbite caused by evaporation of the monomer in contact with the skin and to prevent the irritat ing effect of the phenol in contact with the skin. High conccnration of Vinyl Chloride Monomer vapors can cause dizziness and anesthesia. Persons t displaying those symptoms should be immediately removed to an uncontaminatcd area and the ap propriate first aid treatment given. A physician should be called at once. Areas where Vinyl Chloride Monomer is han dled or stored should be plainly posted as fire hazard areas, and employees should be thoroughly indoctrinated in the safe handling and fire fighting procedures for Vinyl Chloride Monomer and in first aid procedures to be performed in cases where persons are splashed with liquid monomer or show' signs of being affected by high vapor conccntra- tions. These first aid procedures and handling and fire fighting procedures arc rather thoroughly out lined by the Manufacturing Chemists' Association .in their Chemical Safety Data Sheet SD-56, and it is recommended by Monsanto that all users of Vinyl Chloride Monomer follow those procedures. .\ ! .. . u4O 7 TV..a .hiwmiitiOu contained in ihx bulletin if, to our htit knowledge, and accurate, but alt rcromirtenriationi or iug*p*liom Ktuit without guarantee, unco Uio cinJ.i.j.-.i use arc bc/onct our contxob To* Mon*oQ Chemca* Cosv.finy duclaimi any iiAonir/ incurred to connection with Uie uac of were bat* or sugjciuont. o oonttbacb be/eta Wm.'A ceaiuuwd aa * ffvvT-F"u-*-llAr- to u*a uy product to owubcc w|jb patent* cavrug any maUnab or Ua uae* MONSANTO Ci-luMJCAL COMPAMY Hydrocarbons Division ST. LOUIS. MO. S3U6 aTlaNTa, GA.. Peacht/rc Road N.B, :C;TON. MASS., Zvtreu fiitL.oo *<3 CaiCaGC, ivt., 2)29 N. MicniSan Ave. CINCINNATI, OHIO. 2330 Victory Parkway CLcVcLaNO. OHIO. 3GiS Warrenviilfl Center Hoad DSTiGiT, MiCH.t Northlano Tow*r HOUSTON. TC-XaS UOl South Coaat Building LOS anGLS, Cal,. *670 2. Flotilla Blreat MINNEAPOLIS, MiNN,, Ptthay Tower Bid*. NeW YORK. H. Y, Par* Avenua mTSiuAGH, fA*, i Qauway Center ST, LOUIS, MOn Undker;n and Oliva 5L R4. Santa Clara, Cal.. :t;j h-.'iyme Street SEATTLE, WASH.. Sll Weatrrn Avenue WSPILRMINIGNFGIETLODN. ,MDASU**, ESM13* MCoonmcoarnduPiAkveenue li i i ! ! ! 1 Ml! M - t-v ` 1 1H | | 1 ?J ! 1 1y1 5***--1 V'DiYH. CHLORIDE MCNOiWEE Chorrtical and Physical Data Structural Formula: CKssCKCl Molecular Weight: e2.50 Physical Stato: Gas at ordinary temperature and oressuro.'Liquid in cylinders or other pressure vessels at room temperature Color of Gas: Colorless Oder of Gas: Pleasant, sweet Reactivity:, Polymerizes in presence of air, sun light, oxygen, or heat, otherwise quite stable Corrosivity: Non-corrosive at normal tempera ture when freo of moisture. Accelerates cor- rosier* i*i ct with H30 at elevated temp. Boiling Point; -12.9C. (7.0F.) Hygroscopicity: None Critical Pressure: 52.7 atm. Critical Temperature: 153.4 C. (3I7*F.) Entropy; S = 63.03 cal/C./mol Explosive Limits: 4-22% by volume FlashPoInt: -7SC. (-10S.4"F.) Freezing Point; -153.71 "C. (-345-F.) E.eat ot Comnusuon ^G.oss). Gas: 2S2.3 keal/mol (constant pressure) Heat cr r ormation: a_ = 7.5 l;cal/mol (gas at 25 C.) 4.1 heal/mol (liquid at 1SC.) Heat 0. r us.on; AH -- 1.131 hoal/mol at -159.7'C. Heat of Vaporization] A H -- 5.5 keal/mol at 13.9*C. Esdmatod Latent Heats of C3H3CI Latent Heat (Clapeyrons Equation) *c. cal/g keal/mol -20 33.4 5.52 0 31.4 5.07 20 77.7 4H5 50 ,70.1 . 4.33 Ignition Temperature, autogenous; 472.22'C. (332*F.) (Vapors above at -60* C.) Index of Refraction: 1.3S at 15*0. Vapor Density: 2.15 (Air -- LOO) liquid Density: Temp. aC. -12.96 1.32 13.49 . 2S.11 39.57 43.20 59.91 Liquid Density g/cc 0.9692 0.3443 0.9223 0.3955 0.S733 0.8555 0.3310 - ,d (g/cc) -- 0.9471 --0.001746t (*C.) -0.00000324^ MONSANTO CHEMICAL COMPANY Hydrocarbons Division. * St. Louis, Mo. 0 Solubility iu; Water Alcohol Kerosene "Heavy Solvent' Slightly Soluble Soluble Very Soluble . Soluble Soluble Dichlofoothano and Ethyl Alcohol: CsHiCJa CrfOH 73177# 11g g/100 g 0/ solvent (0`C.) 400 2GB 300 16,7 200 10.5 , ICO 5.25 17B 12.1 . S.C5 3.73 Specific Heat or Liquid: 0.2.7 cai/g/C. or BTU/lb./*F. S*oocinc Heat of Va*oor; TOe/m" v... * 25 127 227 3'O2'7?1 527 Sp^cipc *7<3c* esi/grc. 0.2C3 0.249 0.2S5 0.314 0.337 QBSS SpociSc Volume: Estimated Specific Volume of Saturated Vapor of Vinyl Chloride Temp. c. Specific Volume cc/g -30 . r --20 0 20 40 60 635 41S 199 105.4 60B> 33B Vapor Pressure: Temp. o ur*, Press. cm Hg Press. aim . -2S.73 -13.61 - 1.57 S.S3 25.72 39.72 30.34 39.56 67.76 122.48 153.20 302.70 ' 449.60 759.50 0252 0.S9 1.61 2.0S 3.9S 5.91 9.99 Log p *= 0.3420 --1150.0/T 1.75 lo^T --0.002415T da = atm. absolute T =3 temp. C. absolute Viscosity; Liquid: QBSi ceatipoises at --20 C.* 0.263 ceatipoises at --1Q"C. -r a^-0Q "\*i .'r.i'iSfrriAtiftr. contained in th* bulletin n. re our heat knowledge, tnie And accurate, but *11 recommendation* or *uCSe*tion* are mad* without guarantee. finer tne c.r.id.wAi.i c.i uc wrc beyond our control. The Monfanto Chemical Company ducium* any Lability incurved in connection with the use of the** data or tug^oUon*. *wrtdr*ncr*t tuo)u.j comamed hcr*u wtaii b construed m a lanQuarabatioa to u* any product u coaoact with twtifiS patent# wvtnoj any aatinait or iu \u. MONSANTO CHSMICAL COMPANY Hydrocarbons Division ST. LOUIS, MO. Uuj.1*. ca.. 53;) Pf.e.V.re, Rota N* HOSTON. TEXAS lio; South Co**l Building ST, LOUIS. MC,, Lindbergh and Olive SL. Rd. SC S' Cn . maSS., Zvercu Station <* LOS ANGSLES, CAa.. *670 S. Tlotilla Street SaNTA ClaSa' Cal., 2710 Laiaycuc direct CCI^NiCCmaNGNCa,T;I,LLO.,riillOl-. f:t3.5Mb icVh.cigtoarny APaer.kway JQ CL7*v0iL*7A.hOM.iCOtiH.,IOA.W3CN4oSrtWhlaarnrdcnTivotwileer#Canter Road MiNNcAPOUS, MiNN., rothay Towr Bldg. NEW roax. N. Y. 44S Parte Avenue PlTTSaUA&H, pa., e Galeway Center SEATTLE. Wam., all Wcatcrn Avenue $?AIN6F<l2. MaS,, 22 Montana avenue WILMINGTON, dU Concord ?ike ;; i\ * i- * LrGJIHD:, r-< 1 D t;l N O T (i`vi) X< it H PI *1 Vc ivl U j:j i o a r.) i n g 5 ~i ~ o1 ^A G r: *" .........* . - GAT L V/M-Vi Gl.OBi: ' /J CHICK, " DIAL TYPE PRESSURE 1 ND1CATOR SAMPLING POlN T 1A g f\ a m ;' t O lV t? PUMP Sl.rr; CD-tO Manu/teiurinc CSunau' Auoei-tisn, Inc. Vinyl Chloride 1.3.5 Valve protective caps should be kept ir. place or. cylinders except when the cylinders are connected for discharge. 4.3.5 Cylinders must not be filled except by or with the consent of the owner, and then only , in accordance with the Regulations of the In' terstate Commerce Commission. 4.3.7 No attempt should ever be made to' mix gases or liquids in a. cylinder.. 4.4 Tank Cars 4.4.1 Applicable,instructions for unloading tank cars containing flammable liquids are set forth in MCA Manual Sheet TC-4. (Also see ICC Regulations, Sea. 74.550 to 74.563 inclu sive, for unloading tank cars.) 4.4.2 Shipper's instructions should always. 1 be followed and all caution markings on both sides of tank and dome should be read and observed. 4.4.3 Ir. the event of a tank car fitting fail-. ure or leak, the shipper should be telephoned o0^ .ro6)' w. ired' immediately for instructions (See 4.4.4 Tank cars , should be electrically grounded to dissipate static or induced light ning charges. 4.4.5 No heat should be applied to the tank ear. An inert gas line or compressed vinyl chloride gas line should be attached to vent connection of the tank car to provide a pressure for transfer of the liquid vinyl chloride from tank car to receiving tank. Cylinder nitrogen (inert gas) is often used as the pressuring medium in the event vinyl chloride gas is not available. Larger in stallations may have a suction line connected from, the storage tank to a compressor.-which discharges compressed vinyl chloride gas to vent connection or. tank car. The pressure on the car should never exceed the service pressure a; which the safety valve is set to operate. 4.4.5 Some tank cars ir. vinyl chloride serv ice are equipped with excess fiow check valves. A too rapic opening of the discharge valves will cause the check valves to close. If this should occur, the outlet valve should be closeduntil the pressure is equalized and the excess f.ow valve opens. 4.4.7 Positive vinyl chloride or inert gas pressure should be left in car. No air should be allowed to enter car (See 3.3.3). 5. STORAGE 5.1 Hazards (See 8. Health Hazards and Their Control) _ 5.1,1 Aside from the risk of fire and explo sion, vinyl chloride presents no other very seri ous problem in general handling. The presently accepted upper limit of safety as a health haz ard is 500 ppm. 5.1.2 Vinyl chloride should always be handled with full recognition of its fiammability. Precautions should be taken both to keep the material enclosed and to eliminate sources of ignition. If there should be any unavoidable leaks, reliance must be placed upon the elimination of all sources of ignition and or. the provision of sufficient ventilation to keep escaping vapors at nonflammable levels (See 6.2). 5.1.3 CORROSION Vinyl chloride is noncorrosive at normal atmospheric temperatures when dry (moisture free). In contact with water at elevated tem peratures vinyl chloride accelerates corrosion of iron or steel. 5.1.4 VOLATILITY Vinyl chloride is very volatile and is a gas a: normal atmospheric conditions. Containers used for handling vinyl chloride at atmospheric temperature are always under pressure. 5.1.5 TEMPERATURE REQUIREMENTS Inhibited vinyl chloride may be scored at normal atmospheric conditions in suitable pres sure vessel. Uninhibited vinyl chloride may be stored either under refrigeration or at normal atmos pheric temperature in the absence of air or sunlight but only for a duration of a few days. If for longer periods, regular checks should be made for the presence of polymers. 5.2 Conditions of Storage 5.2.1 TYPE OF CONSTRUCTION A'.', piping (including instrument leads), storage tanks, relief devices and equipment employed to handle vinyl chloride should be of steel and designed to have a working pressure o: at least 100-150 psi with a safety factor con forming to the A.S.M.S. code for unfired pres sure vessels or any code applying to locale of planned storage. Shut-off valves and control 3