Document YrgYyJvo6493qkKwrk2B5x9Bn

1-8 OPERATING MANUAL AMS EMERGENCY KILL SYSTEM ABERDEEN PVC PLANT September 1, 1981 FINAL ISSUE Work by: /J. Richard D. Mel ling Senior Process Engineer Chemicals Division Process Engineering Department VAB.0001132824 Interoffice Communication To C. L. Miller, Aberdeen, Mississippi From R.D. Mealing, Ponca City, Oklahoma Date September 1, 1981 Subject Emergency Kill System Operating Manual The final issue of the Emergency Kill System Operating Manual is attached. This issue incorporates comments and suggest ions from the August 18 plant review meeting. /J Richard D. Mel 1ing Senior Process Engineer Chemicals Division Process Engineering Department ms Enc CC: RAF:SJV:PEM:JAD:MPB CRM:JAB:JLW:JHM File: A-20.3 * VAB.0001132825 1-8 TABLE OF CONTENTS OPERATING MANUAL AMS EMERGENCY KILL SYSTEM ABERDEEN PVC PLANT Page No. I. INTRODUCTION........................................................................................................................ 1 A. PURPOSE........................................................................................................................ 1 B. OPERATOR RESPONSIBILIT IES............................................................................... 1 C. PROCESS INFORMATION................................................................................... . . 1 II. GENERAL PROCESSDESCRIPTION ...................................................................................... 3 III. SAFETY....................................................................................................................................... 5 IV. OPERATING PROCEDURES........................................................................................................... 8 A. INJECTION PROCEDURES......................................................................... 8 B. ROUTINE OPERATION ................................................................................................. 12 C. TESTING PROCEDURES..................................................................................................... 15 V. APPENDIX......................................................................... 17 VI. PS! DIAGRAMS............................................................................................................................26 VAB.OOOl 132826 Page 1 1-8 . INTRODUCTION A. Purpose The purpose of the Emergency Kill System is to increase the re liability and effectiveness of equipment and procedures used to safely and quickly stop the polymerization reaction in the reactors. Stopping the reaction prevents excessive pressure buildup which can cause emergency releases through the reactor relief valves. This system allows any or all reactors to be shut down in an orderly and safe manner. This manual describes the system and the operator's responsibi1ities for operating and maintaining the system. B. Operator Responsibi1ities The operator is responsible for producing quality products in a safe and efficient manner. He fulfills his responsibi1ities by knowing the following and passing a written exam: 1. Understanding how his equipment functions. 2. Understanding what role each piece of equipment plays in the process. 3- Keeping a close and regular check on equipment. 4. Knowing how to spot malfunctions and correct them. 5- Keeping his area of responsibi1ity safe and clean. 6. Keeping complete and accurate records. C. Process Information The polymerization reaction of VCM to form PVC gives off heat and accelerates as temperature increases. As the temperature increases, the reactor pressure also increases. It is there fore necessary to remove the heat of reaction with cooling VAB.0001132827 Page 2 INTRODUCTION (CONTINUED) C. Process Information (Continued) water in the reactor jacket and condenser. Reactor agitation is also required to maintain uniform reactor mixing and efficient heat removal. If reactor cooling and/or agitation is lost, the reaction must be stopped. Failure to do so would result in a runaway reaction with increasing temperature and pressure. The reac tor pressure could increase until the rupture disk/safety valve assemblies would vent the reactor contents to the atmosphere. The new Emergency Kill System provides the capability of in jecting up to 25 gallons of killing agent into each reactor either remotely from the control room or manually at the re actor top head platform. Killing agent can be injected into a reactor as soon as agitation is lost to take advantage of mixing caused by residual swirling motion. Maintaining cool ing water flow after loss of agitation will also help mixing by refluxing in addition to removing heat of reaction. VAB.OOOl 132828 Page 3 1-8 GENERAL PROCESS DESCRIPTION Refer to tfcte attached P&l diagrams for the complete system layout for each reactor area. Emergency kill injection pots are provided at grade level for each reactor. All injection pots are to be maintained at 300 psig pressure using high pressure nitrogen cylinders. A separate nitro gen cylinder and spare are provided for each injection pot. Level gauges and pressure gauges are provided on each pot in addition to board-mounted low pressure alarms and low level indicators. The A operator should check the appropriate injection pot level and pressure before starting each reactor charge sequence. Killing agent can be injected into the reactor either remotely by the lead operator or locally by the A operator. Normally, the emergency kill system will be activated from the board to minimize time and maximize mixing. One switch for each reactor operates automatic double block valves at the reactor top head level. Placing the switch in automatic mode opens the valves and allows a low level switch in the injection pot to close the valves. Placing the switch in the momentary-contact manual mode also opens the valves but the valves close when the switch is released. Each injection pot low level switch also activates a local light at the manual injection point at the reactor top head level. The auto matic closure of the remote injection valves and the local low level indicator light are provided to prevent nitrogen from being injected into the reactor, blanketing the condenser and reducing cooling efficiency. VAB.0001132829 Page A I I. GENERAL PROCESS DESCRIPTION (CONTINUED) Emergency Injection headers are provided at the reactor top head level in each reactor area. These headers will allow any injection pot to be used to kill any reactor in each area or to inject additional killing agent if needed. The procedure requires two hoses, one to connect an injection pot to the header, and one to connect the header to the reactor. Killing agent can then be in jected locally by the A operator or remotely by the lead operator. It should be noted that when the emergency injection header is used, the injection pot low level switch will neither automatical 1y close the remote injection valves nor light the appropriate local indicator light. Caution should be taken to prevent charging nitro gen into the reactor. The remote injection automatic valves will be operated by nitrogen supplied by a high pressure nitrogen cylinder and spare. A boardmounted low pressure alarm is provided for each area to alert the board operator when the cylinder in use has dropped below 600 psig. A cylinder with less than 600 psig pressure does not contain enough nitrogen to operate the control valves and should be immediately changed out with a full cylinder. A Page 5 SAFETY The operation of the emergency kill system does not present any extremely hazardous situations. In fact, it's main purpose is to reduce the potential for having hazardous situations in the reactor area. However, some potential hazards are present and precautions should be taken to prevent serious incidents. A. The killing agent AMS has been in use for some time in the plant and the operators should already be familiar with the corresponding safety hazards and proper handling procedures. The attached vendor literature describes chemical properties and safe handling procedures. It should be emphasized that AMS is highly reactive in the presence of the peroxide ini tiators used in the plant. AMS AND INITIATOR SHOULD NEVER BE MIXED UNDER ANY CIRCUMSTANCES. B. The new AMS injection pots will be maintained at 300 psig by high pressure nitrogen cylinders. Due caution should be exer cised in the handling of nitrogen cylinders. Operators should avoid damaging the outlet valves on these cylinders. The AMS injection pots will contain AMS under 300 psig pressure, so proper safety precautions should be taken while working with or near these vessels. The injection pots must be depressurized before the block valves on the pot funnel or AMS fill line are opened. The nitrogen supply to a pot should be turned off at the pot prior to vent ing the pot. The pots should only be vented through the bleed valve on the pressure gauge/pressure switch piping on the top of the pots. POTS SHOULD NEVER BE VENTED THROUGH THE FUNNELS ON THE SIDE OF THE POTS. Page 6 1-8^ SAFETY (CONTINUED) C The rupture disk and relief valve assembli es for each injec- tion pot are set to relieve at 400 psig, the vessel design pressure Since nitrogen bottle regulators occasionally 1 eak through, a potential exists for overpressuring the injection pots and causing the rupture disk to burst, Even if the killing agent didn`t spray out when the relief devices opened, it is probable the relief valve would not completely reseat and the n itrogen bottle would slowly depressure through the pot and relief valve to atmosphere. The outside operator should routinely check injection pot pressures to insure it is neither too low nor too high. The AMS killing agent is a volatile hydrocarbon, and thus fire D. and explosions are theoretically possible. Precautions should be taken to prevent spills and excessive accumulation of flam mable vapors. E. Since the injection pots are connected to the reactors, a poten tial exists for backing VCM into the pots. This poses no se rious immediate problem since the AMS would kill any reaction that was occurring However, it could present an exposure problem later when the injection pot is opened. The injection pots should be maintained at 300 psig pressure except when re- filling.1 \ I 1 l I i cj * Finally, operators should keep in mind that this system will F. be used when the plant is in an upset condition, i.e., power failure, loss of cooling water, reactor runaway, etc. It is VAB.0001132832 Page 7 SAFETY (CONTINUED) critical that this system must operate properly in such an emergency. System maintenance and operator familiarity with this system are equally important factors ensuring the dependability of this system. * VAB.0001132833 I-** Page 8 OPERATING PROCEDURES A. Jnj.ection Procedures 1. The emergency kill system should be activated under the following circumstances: a. Extended loss of cooling water to a reactor in poly merization mode. b. Extended loss of agitation to a reactor in polymeriza tion mode. When agitation Is lost, it is Important to kill the reaction as soon as possible. The reactor contents will continue to swirl for about four minutes after agitator shutdown, and AMS injection during this period is much more effective. c. A runaway reaction with Increasing temperature and pres sure which is not responding to small AMS Injections (short stop) from the initiator charge pot. d. Any other circumstance considered by the operator to represent a significant chance of over pressuring the reactor or affecting safe operation of the plant. 2. The emergency kill system must be activated If the reactor reaches the following pressures for the following products: a. 5305 with CTA 155 psig b. 5305 without CTA c. All other products 165 psig 145 psig 3. Lead Operator Duties a. The lead operator should remotely inject AMS into the polymerizing reactors which require killing by placing the appropriate hand switches in the AUTO mode. VAB.0001132834 Page 9 OPERATING PROCEDURES (CONTINUED) A. Injection Procedures (Continued) 2. Lead Operator Duties (Continued) b. The lead operator should then check for confirmation of AMS injection from the board-mounted low level indicat ing lights, and from the A operator via radio. In jection time should be about 30 seconds. The boardmounted injection pot low pressure alarms will normally be tripped during AMS injection. If the pressure and level alarms are not tripped, the automatic AMS injection line may be plugged requiring manual injection. c. After AMS injection, the lead operator should closely monitor the reactor temperature and pressure. If cool ing water has been lost, he should take steps to restore cooling as soon as possible. d. If additional killing is required, the momentary-contact manual switch can be used. Caution should be exercised to prevent nitrogen from entering the reactor and blanket ing the condenser. e. If excess nitrogen does enter the reactor, the condenser should be vented to the recovery system. 3 A Operator Duties a. The A operator is responsible for field-checking AMS injection to each of the reactors to be killed. He should confirm that the injection pot level is at the low level mark on the level gauge. Too high a level Page 10 I-# IV. OPERATING PROCEDURES (CONTINUED) A. Injection Procedures (Continued) 3- Continued) means not enough AMS was injected. No level may mean nitrogen has entered the reactor. b. The A operator should also check the pressures of the nitrogen cylinders used for AMS injection. Any cylinder with a pressure lower than 750 psig should be changed out to allow for a second AMS in ject i on. c. After checking the injection pot and nitrogen cylinders, the A operator should proceed to the reactor top level to confirm that the automatic injection valves are closed. If the valves are open, he should man ually block in the line and inform the lead operator that nitrogen has entered the reactor. It may be necessary to vent nitrogen to the recovery system to maintain reactor cooling. d. If the automatic injection system failed to work, the A operator should manually inject AMS to the re actor. He should open the manual double block injection valves, wait for the injection pot low level indicator light to light, then immediately close the double block valves. The valves should also be immediately closed if the line begins to vibrate from flowing nitrogen. VAB.0001132836 Page 11 OPERATING PROCEDURES (CONTINUED) A. Injectron Procedures (Continued) 3. A Operator Duties (Continued) e. If additional injection is required, the A operator should prepare the emergency injection header for use. This header is supplied to allow any injection pot to be used for any reactor. This is accomplished by connect ing one hose from a full and pressurized pot to the header and connecting a second hose from the header to the appropriate reactor. Injection can then proceed either locally or from the board. Caution should be exercized when using this header since the injection pot low level switches will not work correctly and nitrogen may enter the reactor. f. As soon as possible after injection, the A opera tor should refill the empty AMS pots and prepare for a second injection if needed. 1. Close the block valve on the nitrogen supply line at the pot. 2. Depressure the pot through the pressure gauge vent valve. 3. Refill the pot with AMS from a 55-gallon drum using the air operated drum pump supplied with the system. An alternate filling procedure is to manually pour AMS into the funnel on the side of the injection pot. VAB.0001132837 1-8 Page 12 A OPERATING PROCEDURES (CONTINUED) f\. Injection Procedures (Continued) M 3. A Operator. Duties (Continued) f. (Continued) 4. Block in the pot and repressure with nitrogen from the nitrogen bottles. g. Radio communication between the lead operator and the A operator should be maintained. The A operator should inform the lead operator how the system is operating and what is being done in the field. The lead operator should keep the A operator Informed of reactor pres sures and any apparent need for additional AMS injec tion. B. Routine Operation 1. A reactor should not be charged unless its AMS injection system is in proper operating condition. It is the respon sibility of the A operator to check this in the field and notify the lead operator prior to each reactor charge. The following items should be checked immediately before each charge: a. The AMS level in the injection pot should be at the full mark on the level glass. b. The pressure in the injection pot should be 300 psig. This should be checked both on the injection pot pressure guage and on the nitrogen cylinder regulator outlet pressure guage. VAB.0001132838 Page 13 A OPERATING PROCEDURES (CONTINUED) B. Routine Operation (Continued) c. The block valve in the AMS line near the injection pot should be fully open. d. The block valve in the AMS line at the reactor top head level near the hose connection should be fully open. e. Both block valves on the manual AMS injection line should be fully closed. If any of the above conditions are not met, they should be corrected before the reactor is charged. 2. To insure proper operation of the system, the following items should be checked by the A operator at the beginning of each shift: a. The pressure of the nitrogen cylinders being used for AMS injection should be at least 1200 psig. Cylinders with lower pressures should be changed out with full cylinders. EMPTY BOTTLES ARE NOT TO BE LEFT IN THE BOTTLE RACKS. b. The pressure of the nitrogen cylinder being used to actuate the automatic AMS injection valves should be at least 600 psig. Cylinders with lower pressures should be changed out with full cylinders. The pres sure on the outlet of the regulator for this cylinder should be 100 psig. l VAB.0001132839 Page 14 OPERATING PROCEDURES (CONTINUED) B. Routine Operation (Continued) c. The pressure gauges between the double block valves on both the automatic and the manual injection lines should routinely be bled to 0 psig. If pressure sub sequently builds up on these guages, it indicates that one or both of the double block valves are leaking. Note: These gauges will have pressure on them after AMS injection. d. All spare nitrogen cylinders in the racks should be full, i.e., cylinder seals are intact. The above items are vital to the proper operation of the emergency kill system. If any of these conditions are not met, they should be immediately corrected. 3. Other items which should be checked on a routine basis are: a. The automatic AMS injection line reactor nozzles should be checked for plugging. This can be done while the reactor is being rinsed. Full port ball valves have been provided on this line so that a rod or long wire brush can be run through the line to knock out plugging. This line should be checked once a week when the system is being tested. b. The manual AMS injection line reactor nozzles should also be checked for plugging on a weekly basis. This should be done in a manner similar to that used for checking the automatic injection line. Page 15 * 1-8 IV. OPERATING PROCEDURES (CONTINUED) C. Testing Procedures 1 . The AMS injection system for each reactor will be tested weekly on a schedule set up by the process superintendent. Each system will be checked for line pluggage and valve operation. The testing procedure is outlined below: a. The A operator should perform a complete visual check of the system to be tested both at grade level and at the reactor top head level. b. He should then contact the lead operator on the radio and confirm that the reactor and Emergency Kill System are ready to be tested. c. He may then manually inject approximately one gallon of AMS to the reactor by opening the manual injec tion valves for approximately two seconds. d. After AMS has been injected manually, the A operator should close the block valve near the hose connec tion and notify the lead operator that the automatic system is ready for testing. The lead operator may then remotely cycle the injection valves using the momentary-contact MANUAL mode of the control valve hand switch. e. During automatic AMS injection testing, the A operator should be checking for proper operation of the system, i.e., control valves, actuators, and solenoids. VAB.0001132841 Page 16 OPERATING PROCEDURES (CONTINUED) Testing Procedures (Continued) * f. After automatic injection testing, the A operator should rod out the vertical sections of line at both reactor injection nozzles to confirm the nozzles are not plugged. 3. The following must be done following a test prior to charging the reactor: a. The pot should be refilled with AMS. b. The pot should be pressurized to 300 psig. c. The AMS injection nitrogen cylinder pressure should be checked (above 1200 psig). d. The pressure of the nitrogen cylinder used to supply instrument air to the automatic AMS injection control valves should be checked (above 600 psig). e. The manual block valve at the reactor top head level near the hose connection should be reopened. VAB.0001132842 1-8 Page 1 7 APPENDIX VAB.0001132843 STORAGE AND HAN DUNG OP ALPHA-METHYL STPYllENE 1-8 Page 18 Alpha-Methyl styrene Is usually stored and handled in steel equipment. It is also compatible with stainless steel, aluminum, and galvanized iron. Copper and copper alloys are not recommended for this service. This product has a fairly low freezing point (about -10 F) and low viscosity. Underground storage tanks and lines should be considered, as their use will prevent freezing in winter and keep the product cool in summer. Storage temperature should not exceed 100 F. Storage under a nitrogen blanket is preferred; exclusion of air (oxygen) will reduce the chances of polymerization, peroxide formation, and fire. Piping can be of the materials listed above. A centrifugal pump is suggested for transfer service. 11-reflon" is suitable for gaskets and packing. An inhibitor, para-tertiary butyl catechol ( 10-20 ppm), is used in alpha-methyl styrene to inhibit polymerization. If storage time is prolonged, the inhibitor concentration should be checked occasionally and more inhibitor added, if needed. Alpha-Methyl styrene is a toxic chemical; contact with liquid or vapors should be avoided. VAB.0001132844 a- methylstyrene 1-8 A Page 19 * 7M r*1 r. '* * y *i V" fv ir***r CHEMICAL NAME: SY NOHYMS: CHEMICAL FORMULA: O-Methy ] s tyrene Is op rope ny1 benzene, a 1pha-niethy 1s ty rene, 2-phony1 propene, 1-me thy 1-1-phenyl ethylene Cn9H 10 CHEMICAL STRUCTURE: \ ^a riir li >r.,,Vv<Y<my,;c,*-xT` SCi**.*-^'v;*$^5j - H. A y'r' ^ i i ci f i c c . * * ' * 4 Mn. 1 ecu 1 a r weight... ** + *4 l Flammability limits, vol %, upper............................................................ ^1 o^ 1w' ^e^r.. ^ j. . i i i Water-white liquid 113.18 6.1 I l -/ C',~ FI ooft point, open cup, ' ag) . closed cup, C (Tag) . * * * * ft** Autci'jni tior. temperature in air, C................... ................................ 52 (126F) 44 (112"F) 575 (1066F) 165.4 Boiling' point at at 71--060mnmunM.. Sqig , o rC.'........................................................................................ ^IpOp.J. ur Freezing point, ** * Y^por pressure, Hg at 20C. Sol ub i li ty , wt x in water. ;'20c; water in. Specific crav ; > f <- at 20/4C heat of veporu'at rn at 1 atm, Btu/lb. neat c f combustion at 25C, Btu/lb.. Coefficient of expansion at 20C, vol/C......... ft * * * ** * -23.2 1 .9 <0.1 0.1 4 1* 44 *4 * I * 0.9106 \ 140 17,748 0.00096 1\ i 1 r 1 .3 5 ^r ^ fw t ^ *3 *w ^ 4 \ ^ f* lw VJ ^ . ' ir's J *J * ii 4**1* # * 4 4 4* * * 0.94 Revised 3/15/76 VAB.0001132845 (X- Ml. Til V 1ST V Rli'lt 1L -J Page 20 SoT.e significant reactions with the mo re common chemicals are Or"!efly discussed below: <ida tion forms aldehydes and peroxides if exposed to air oxygen). Can be epoxidized and is attacked by strong oxidizing agents. I-8ft i Oroqenfftion l,;n be hydrogenated catalytically in the presence or metals. The unsaturated vinyl group and the aromatic ring can both be hydrogenated under selec r i -ji> r nnrii t i ons . :.al ooenation Characteristic addition to the vinyl group ana substitution on the aromatic ring can occur with nalogens such as chlorine or bromine. These exothermic addition reactions generally require catalysts and/or elevated temperatures and are not considered hazardous if properly controlled. However, reaction with chlorine which occurs at ambient tem peratures can be violent in the presence of light. Accidental contact of CT-methylstyrene with halogens or ha 1ogen-containing compounds must be prevented. Under special conditions, the aromatic ring may be attacked by concentrated nitric or sulfuric acids. Tnese reactions must be carefully controlled to avoid hazardous consequences. Also, hazardous oxidation may occur by contact with concentrated nitric acid. Me rnq xv1 a tion Methyl styrene can be reacted under special condi tions with formaldehyde or CO-1 i2 lne presence of a catalyst to yield an aldehyde or alcohol. This reac tion is considered to be nonhazardous as it is un likely to occur accidentally. H n ^ * c:1 ! t j >i.u ool e r 1 ratio r: " ^r *r L < -i 1' ' V- in ti 1 e pi 1 r \ p ", !'. 1 r >i' I * r J 0/ / 0 , iscussed reactions other than oxidation, ha 1ogena tion, '0 generally considerec to be nonhazardous However, when U or laboratory, all of the reactions of f/-methyl styrene 'n n t y',') 11 r! tn .writ! hazardous - / , i i r n n M A rl r Ci 4 ] c - v.0 customer wants to use rubber hoses Tor unloading tank and steel or' rubber Ins } r recommended materials are Vit.on A or polyethylene lining. v. i qV' A SS fittings. Both Uni royal and Goodyear manufacture with a Viton A or polyethylene liner. _________________ _ r Other elastomers"T~ 1*J* - * such as neoprene, buna-h, etc., are not recommended for handling AMS because they wi11 S i- chemically attacked by the AMS. Another type of hose that Cti n u C i: mc r:* c ' < j n ^ tl SS flexible metal hose. 0 y / f/fs?-/ cr. VAB.0001132846 A-METHYL STYRENE Page 21 T t v i * umrr :k y of exposure iludici on nnlmcsU. Vhir onto indie ok* ihc relative j i t1 Jtr j-vjru m nondi rl `be pr roduct. Incrm'ir. j drqree! of bnrirri cue f* <presi<'rJ j v , :crmi: diqbt, fT'.oticr ife, cleftn:?e, scpou! If must be remembered ibol resell! of exneri::(ur'^ on ammo!; ^onr.ef be numencui y from infect lo prebnbie human response* 11. P! . i e ' , j I j, r * . C a , ._u i * y f n * * Council 01 n n c i t^iicey a v tho ' U p r e Unu, Cr i* mi u r r' ,M jijfd ; \ 1bo prLjt;j. re.o m- >ry v. <1 r i* * o 1l f r o nn me kjmniuuj or ol i' < i.jbbt ; jK? quantify, frequtmn/ end manner ur lyV(* J l J O i ^ 1 r; e f.; c ror impofiaf'l e> iJ < g r i`i c-1 I c :ij; J . bo'eknq a rhe :n = co! o fV - r ; = * -i i'l! ;, ! J' r J ; S Oi the* lh-111'U'i f c r m m i ng ine i'i o prct:ei"d 1 '. g r ! h C r - i1 h f o, !!' !a :\y c I C*pO*urC are e p.-Ol'.y imporlqnl * L it* trm mV; Vn been adopted ns o kOui'am txproi* : 11 cl . w) i e d . i v 1 o * c 11 y for c o n i p a m n g a n r chemical ci.'y'hv*'. 11 r ters Jo that quuneiy V o> cnee at which - o 3j CenI of exposed an*moli. For tuoner uni;or.niiy( . : tn-s oi(- en; re^eti tn granu or milidiieu of chemical ,, e r n^qm"- of a nmal body v*eight. cb-r 'p't* utn pi-ip trur.'m r rfc*o Cl r Qvrn'd 24'houf ikn conicrr w'h thn n:;u d lhen'icol Sinij.c -nhuluhon re feu to continuously breaching a cerium oi'ff r'.ircricn of c S e n i n. a voporj for a ipccifmd pr : ic (1 of !irt.e. p<-itT'ory irrilahor' r>-irri I o th. stin response fo!Iov*:fig unccvruuj ilun cim-v. ' A c u v >1 r t d conitot cun bts e^pedoci to Itave a more e.v'-rc *ttect. Cye injury refer4 to surface damage produced Ly con(cut of jho eye wilh ihe c h c rn u u i, legal reiponub iny *s ovsumed only for the fact that ail ifodios reported here, and ah opinion*, aro those of qualified expert;. Sincle oral dose In rats: moderate hazard. >.1 LDcq = 6.50 ml per kilogram of body weight. For comparison, isopropanol has an LDcq of 5.8A grams/kg Single skin penetration in rabbits: slight hazard. 16.0 inl/kg body weight killed 3 of 7 animals from a 24 hour covered exposure. Thie result suggests that skin penetration in harmful amounts Is not apt to occur. Single inhalation by rats: slight hazard. Breathing vapors in a state approaching saturation in room air for 3 hours killed 2 of 6 animals. Skin irritation, rabbit belly: moderate hazard. Hie undiluted chemical caused redness of short duration on the tender skin of the rabbit belly. Kye injury, rabbits: slight hazard. The undiluted chemical caused no irritation when an excess was instilled in the rabbit eyes. t *r ft H m t a TYPED 5/24/77 e Fcr Further Information Writo To: Industrial Medicine and Toxicology Department UNION CARBIDE CORPORATION 170 l-.u k Avenue New York N Y 10017 t VAB.0001132847 1I >' ^ C) i- v -O cl <;rJ-' V ;j n ' CJ ^ o*t c> * CJ xi ' A U) L* ) CO t~ i r- ul o -- 1 I CJ *"?- r. w'.Nj L1 CD co v' > O tD CO o I I I <o <0 o a o v* ij tj r cn -- o ^ * c> Cj CO r^- O co O < i( -- O O ; <o ld r a CJ o UD O J i < r-^ tnTJ O *< iD on ts* LU o --J O on O^ q cn Page 22 Tcr8 o X/ 1 J3 f'i ro t: O o -O cn r; rr w *r. CJ o CJ CJ Cl k_ Imt'j CJ XI rO rj 03 IT--* * Co. <,o cj * o u ^n. w* c> -O * X o m CJt * 11 n cv v/j un ^ CJ .t,' <*t3 ,, d VI C^' R C- n 4. cj - un CJ EG : V tj .^__ CTr CJ = l O' ___ CJ E *2 *0 o r j cj cj Co >-- CD c> A :r> t r* cn f"3 CJ -- T1 r> \y n r j O l L1J v> fM OJ d i c Ji i i c^ ' Q o - s 2 ir:*. _ cr* 4 I e r w i*> \ o--L-* < rrr: o D /*-- O c> a -~t C ^C a" _ .T i3 ^r^ j : ./ , D '# o c Ci C J T} X CP o ,j CJ C Cj Sr- C d L'l oo VI d n L~> Cj xr\ d -# 1 XJ O n L,*> CJ E O u> o 6 r> Cj o o > VJ TJ D1 ^ :~ O "V C~ -J V~" * M t.1 O * " k- i> ii3 **. ^ f"V xr~i rj n o C3 h c. O O cx i** C* O <L^ " rj l%J *1) CJ * r~o n, rj -h v 3 r <* SO - - -j; 'X C*-- * * #- ' e m a: " o CJ T1 ! , %^ ro * 'j O VJ c.? v <-> 1 t 4 v" U .D J 1 *- * -- * - J ^> W "U "J f) 2r o ,, I) ir c: rs O . L. H *r * r: O * * ^ _ '^ >. C3 IT f' <r c, - X tr - X~ JZ O CJ U ^* -- > ^> , ^ CJ V) Vi o CJ o C ro o CL E CU o CJ d 3 P CJ o, V*. o r ' L^j o * c: O >> cj O e o o rj P rj t; vi r~r o Sc nj <- -C v- t'j X) < o o ^ ra c ^ JO tO <* Q CO Vi !L_ 2.. ~ cl. co oj co <J> V) Cl -I - J * 1-- %, - o VJ c.J "j i CJ 7j CJ CJ L_J C J i *n t r~- '' l Li j Vi - oo > rj CL o o o cn o _j cn r- ^j r ^ tn L i * " CJ o < ^ wO CJ v j C- C - 'C' o o VJ o o o 1^ I C ^ rO c~> o to scn CJ Cl cn c: j o cn c^i '.5 m >* -- ' 11 ui LO r^. CO cn cj ci _o to CJ cn 'v o O c"> o J*? o c - OO o cn rv o'r cn r - D ul o <Z> VJ o O -- o CD )* , CD i* *! * :i n v.*> -r i,i O O cn O J oj O Cl v*n CJ cn n -- -- CO CJ r-. ^ O CO CJ ji n c.1! Cv* vn CJ "J CTj L'l no O co CC* L"* C vi O C~i < cj ci CV i "> Cj Cj *i CO -- < n i/-> o oo o lJ -- o O O in f) n n o cn *- cj m rj '.r* to q iq iij lt> " O C_J <C O . r^ xr C\J vi O IT' t O c -* E! t r j m o co ^- o t : r>. c. c, o l: Cvi / *-- o v. , O -O O O ro o cn vCl O *-- LO CJ LD O c j *x r J o CJ \J J C '> LO cn (m iii r \ *-- CNJ o in in o L'l C*i - C-J < i c~ CJ> C) C '1 Co c* CD -- -d ; . Ci J Cxj ^ J <o 1 <D 5 s i I CJ 1cc:i1 n y ^ v e cuj c_j I O 2 CJ ^5 - ^I do ad r CJ \c: c: c: oo crJ o CJ c IJ C* D ^!O CJ c J. o >w * c p r " r; c. , * *. : c. f > CJ e. X\ r *- ' J ^ -j o ^d L' -- O - JJ r: r; :m i >' -- o ^1 o _^ CJ -X c lj Ci ra fj u0 D f-3 7n c -i -< cn cj n O 2C=J 2 ri XT c; p* * a. Vi rj 32 r J rj Cl -- e* c_ L> Cl CJ o cx CJ 3 2 * uj o 3 OJ j<: * O '3 'o o d O c J S.' 00 cn >>K * cn ?31 cn o C 'J) fj " "O o cj c < -- ^JlJ C*.\ *" '---- -- o. C! -- Etz oc C D Oo t - Dj oQ E cj o c: o o cr "J C ___ n d o. O o d; o rj w- '1? E. > Ci t .o vu , J/ XI ** ~D X , -J -1J ^ V. J V. " ^ _________ _L X rV-^ ^ on LT O i-O O t; c n% d o C_ 1 >< < *L CJ r 1 o * o of T1 O c o CX O Cw - m O r.: -- Ti xi 1 . '. CJ * O 0) cr r: rj -JC f*7 O^ g o C o o cr i+ o CJ r.j c_ n oo c r> d> Cj TJ U flj f\J yO X O S' CJ A3 l T1 rj C* d j r_ 'O Q CI c: no -- CJ TJ cn DO XJ o o xz %. * Cl E o CJ <r O cj CJ O TCJ XL * - DJ o Cj d o p-' ^, S O I4-i on - 'ii V nj a ** o -X - {jr . i? ^ *o Cj O f L cr :--L r ur Cl, oC d -* tz ti m rr l~ - - xj? -- ^ O tov cr- -- ' -r i ^ ' o o d JO tD CJ <"j --' c> <u C l Cj CJ C> c-o k* _ * i j <n LU U.* O :r. Co ^i ' 4- t- 4- o -fr- 4- 4** 4^ -- -<*- ^-- 4*^ <- 4- <L. ry |J I f= s L.1 \t , ^ *i~- j^ r^ i! ^c i1 CO JO d J JD m nr It ;i vn < \j Mill 1 ! CD J n l! in II l -n ci f'- tn CO uO Co III1f i J r- C<* LI LO *0 JJ CO Co CD CJ V o "- L j* ci ^-> r *i i J i*i CD m co -aC Co Ol C J ^o + o CO ) o o in in - cn ___* 2 f'l ^ O iA Cv lA oo CJ 51 > to ^1 C7co Cj p UD Co oo j cn C-* k O <o lD o *r ;nj o o ** c y '-- < Cl l O Cl Cl I O au Co I CD tO !I Cl o <U to cr* f i ! v: A O4 -*j CJ LD Cl in* o O o C^J o -- r-^ Cl CJ VX) o Q ( 11 I CO 1C 11 CO t-D O Co O o CJ xi o < o Vi ,* < D CJ CJ d n ~I- t< jQ 3 , k i. i J 4p 1 p E ^ g nE ^A<B5 .0001132848c II r * < -- n rj _vo'. D -; o r : -i -.' \1>j 17~* TO-> j .J k H. -- * k ; D V> I *y p *^ In 't" ;J ID C. vi D *. .j nc r> * o CJ d^ -* 3a ;. -- V- O --- <LZ rr mm d> *! 4- J4 T& rn w, ~ o -f` n ) * 1 t o* t-/ rr_ iNj *O \* * lO L Cj V5 tl O CJ ^ * g " L' n % Cl r VI -- Ti a u *> O IzL d V '' r*j Cj. _ *U ^ tn Cl t O CJ 1 os -r D .D D O i g Z3 *o o -r co CJ d yo 2: _--Ji :J O c't TO v -- d ^ C Td O ' L- z cr < CT ' PU ,, . " : r\ -- -- or cd : d *- d -I *" f2 r: n n4 ;r "J O^ 1 o^ 4. o*\ -^to>li --- * -. " m* ; : ' '-> CJ o D 1 4 .I k 4 H dd id D" d 5 D 0 Cj c ^ c ;4 + o1 d T3 C) ^o O * : r*. __ c J C a Hr l> o cj r; * V LJ TO Co O CJ CJ -"J V d 1 ri O C.J C j' O X f~i X". o rV-i CJ CJ Ci k Cj 4 X. i .V d rj o o c Cj C < _3_ O o v ,:j n tr xr Cj O u V" 4 * LJ 4- 4- . ' ; fl I-. i` * %* * i * * j ' * - *11 * - * J* 4 ` * MATERIAL SAFETY DATA SHEET iApi-rovL'i oy u S OouaMinc-n nl L U)Of '' in* nt n l1 v Si'Tvior1' to Four, LS6 COS 4) PRODUCT MAME: aloha- M ET H Y LST Y R E N E - * # * 4\ Page 23 ,i~8 J sJV *4 CHEMICAL NAME. CHEMICAL FAMILY Aryls FORMULA: C.HcCfCHJ:CH, MOLECULAR WEIGHT 118.18 SY NONYMS. Isupropenyibonzenr?; *-methylstyrene; 2-phcnylpropene; 1-methyl-1-phenylethylene BOILING POINT, 760 mm. H<j PHYSICAL DATA Ja fc 165.4C.(329.7 JF.) FREEZING POINT SPECIE 1C GRAVITY (H30 IJ VAPOR DENSITY (air =* 1) PER CENT VOLATILES BY VOLUME APPEARANCE AND ODOR 0.9116 at 20/20 C. VAPOR PRESSURE AT 20C 4. 1 r 100 i SOLUBILITY i IN WATER. % by wt EVAPORATION RATE ) (Butyl Acetate = 1) Cuiuriess liquid; characteristic odor. f* * HAZARDOUS INGREDIENTS MATERIAL Me tli y I sty re ne * -^ O 100 (See Sections ill through VIII) -23.2 C r- m > Jn * 1.9 mm. Hq 0.06 0.22 L # - * * TLV (Units) '100jprpm. ceiling i -t y A 4 -- -- >-- X/ys ' ) / J.-. ____ di / ^- m ? Y- i --/_ ct L ASH PC I N ,\ ' * <J * ncthodU) I FIRE AND EXPLOSION HAZARD DATA 1i2F.. TaQ clused cup ASTM D 56 126F,, Tay open cup ASTM D 1310 flammable lim vi Or i r AIR, U t. , . .. ' U . Hi ' LOWER j 1.9 UPPER t 6.1 L. \ i NGO'iSHINK lC M l D IA Use carbon dioxide or dry chemical for small fires. Use loam (alcohol, polymer, or ordinary) for laigc fires. SPECIAL FIRE FIGHTING I Self-contained breathing apparatus should be available to firemen. PROCEDURES ' UNUSUAL FIRE AND t XPLOSlON HAZARDS 4 1 ii I No fie EMERGENCY PHONE NUMBER 304/744-3487 Ttus nucntizr is ov,i,iat;;c Jjys, nights, weekends, and holidays ,v uiwh Cw-U'Ut.' Cor^O'JiiuM Uc*j< *vi c - Cu' i ccni.imccl hcmn are factual and the e*urtsscd are those Ol qu1l*e<3 Caperts regarding the results of iesls ; r c,,, iv (i !?',|* C-.iUi ate not iu DC uMfn .i * v .< tV - r r D'eseniauon M which union Carbide Corporation assumes tega' responsibility They are offered solely lor your considOrahOn ,, ti,un ,i,u ve/Tc.Mton *' y w.t_* ui Hu-yi .i i: j.'V. >nU)n)utioh must be determined ty Hm user to be `O ^ccoroaiK 0 with applicabtc Froerat, Stale, anu local laws and regulations ------- ^Mr.nnincrnppmtATinM CHEMICALS AND PLASTICS 2 70 PAR K A VE NUE, NEW YORK. N. Y. 1001 7  r t + t V * . i-- w,, " ; .r - * * * ip ** * 4 ii aI ^ 1 U*.* (' threshold limit value w IV. HEALTH HAZARD DATA 'J f 1 100 ppm. - not to be exceeded. Value from ACG1H (1976) Page 24 1-8 * i i-FECTS OF OVEREXPOSURE Vapors cause irritation of eyes, nose, and throat. Headache, nausea, and vomiting may occur. Eyes are irritated by the liquid. Divergency and first AID PROCEDURES Remove to fresh air and call a physician. In case of contact, flush skin or eyes with plenty of water for at least 15 minutes. Call a physician for eyes. m fc *.'***- m * STABILITY UNSTABLE STABLE \/ - r f* '* ^* * Vi REACTIVITY DATA tI CONDITIONS TO AVOID Avoid heat and open flame ^COMPATIBILITY materials to avoid) Avoid contamination with oxygen, strong acids, chlorine HAZARDOUS '> E C 0 M P 0 SITIO N PRODUCTS Burning can produce carbon monoxide and/or carbon dioxide. \A ZARDOUS POLYMERIZATION May Occur VVi!I not Occur ! CONDITIONS TO AVOID Avoid contamination with peroxides, strong mineral acids, metal halides, and similar polymerization catalysts. Parn-terti3ry butyl catechol is used as inhibitor; maintain its concentration at 10-20 ppm. rEPS TO BE TAKEN - MATERIAL IS RELEASED )f\ SPILLED .A5TE DISPOSAL METHOD -: ** br Wear suitable protective equipment. Collect for disposal. Toxic to fish; avoid discharge to natural waters. Sec Section VIII. Incinerate in a furnace where permitted under appropriate Federal, State, and local regulations. Absorb on paper, evaporate on glass dish, then burn paper. u .0001132850 VII. 'CSPlRATCRY PROTECTION I i :-n:. f y' t/ocj SPECIAL PROTECTION INFORMATION Airsuppliod mask m conf ned areas Page 25 n*8 r*rr JI * V ENT ! LA f (ON i LOCAL EXHAU5T 1 \ * 1 MECHANICAL (r.e:. trail '.lay be needed \/ special O THE id PrlE^t CTIVl GLOVES Rubber EYE PROTECTION Monogoggles J MM K PRO rtCTlVE .ljoip.MEN i Eye bath and safety shower 4* i \ i\ i ,4 ACTIONARY LABELING VIII. i1> .t SPECIAL PRECAUTIONS 4*l-i hi *. . h IP-' i p pI i" *. # it a/p/>a-METHYLSTYRENE DANGER! CAUSES BURNS COMBUSTIBLE Do not get m eyes, on skin, on clothing. Keep away from heat and open flame. Avoid breathing vapor. Keep container closed. Use with adequate ventilation. Wash thoroughly after handling. F IRST AID: In case of contact, immediately flush eyes or skin with plenty of water foi at least 15 minutes while removing contaminated clothing and shoes. C.i:i a physician. Wash Nothing before reuse. FOR INDUSTRY USE ONLY handling and ,:rage conditions Store under a nitrogen atmosphere; forms acetophenone, aldehydes, and peroxides if mr rf er c c. 3 a g rous concentrations of peroxides are not expected to form in norma! storage and handling, but storage under a nitrogen atmosphere is recommended. This chemical floats on water, is resistant to rapid biodegradation, and is highly toxic to aquatic life. Spills should not be flushed to sewers or waterways. The preferred method of disposal is to dilute with a non-reactive solvent or fuel stream and incinerate. Ground areas can be covered with sand or sawdust after most of the spilled material has been removed. Absorbing materials, after use on small spills, should be disposed of in an unproved chemical landfill or by burning. C/NUTION; Do not use clays, micas, or acidic materials which might catalyze . ) / wnerization. as absorbents. Personnel engaged in disposal work should avoid contact of wastes by wearing propei protective clothing. VAB.0001132851 t 93 * --v^^*3rc; ^ > -s; i i I l s: cj /i {>v ^ "* t. j H 4CJ -4 ^ -- -J 'CJ .*.r s /V3 J * . s*i 4| *1 4 i i its 4. > h I ,, * fe w ^ ^ > r * - fi ii j v< 4 * 1 1-4 *. - * ' H 4 . *t 1 hA, . , * ll hi i, I. , #*, ri . * * . <.* r Vt * it-. * * * h *.* -* , . p | * * a Vtf I- . ^ V* 4 , . IV | I J -r I ,* w y J ' i M > 4 lb I - I t * I 1*i 1-V few 4b | , fri 1 I- 4 - >fe *tTi I 4^ * I k i p- I -* i # * ,.p p P '. * _b i *'*** # . , * * i + * i Ji 4---I p pj I i (4 1 ** ^ I . w k< , 1 p- P - k _U m V'* i, *- H ! ^-1 * ..*<* I* >*.# i< t P *I [ t* * # + *-4- *- -V # i- 4 ' , , !! p| il J't*ct_ I I I " * 4I * tfe t | * B W#feJ i | "V #i * . <. , rv * . *, 44 pf>r JV* t 4 * < ^1( < ! *t *P | j0 fp fe - pvt i m i* p l< i4 V t| i II * d* * ` B I* B * . t #- , V P**" V* . * -. V*J| -4l*-l. ** 4-.PB 4 I t I I :: " **it :r=r.:;v3 * - I- r5" '*"3 P f -I'li- ^5af4r it.. >. t r- t " * t* >*ib Lai4.V :^J *1 r> i * # * -i*>3 rwt k| I-.-.4- |. | B*M sfflr \ aVvj i W*9 V.KB.9001132853 Page 27 * [. HC>Xi/VsS OX '* 1 % '/ I \ II 1 t dOlS NHb bC*0*i m /1 *i l: v :t : : ,4p L y. .--y 1 :j^ * *V*- ii -I N J ctO I r-- -- ^ ; --I t L iA L ! rs rtT a l s _1 ** : fc I o>> -I * L1 i 1 L >j is'f. i ^ j IN i V k h I t4 [ SIN3A 1 1 J <fc||ip -a^hp.iE t ii r tb 4 t ! VAB.OOtjj, 152854 oo $ Page 28 t 1-9 * # k VAB.0001132855