Document wD6kR8qeBz8xerYnyQp23ynvD

MONSANTO COMPANY - PLASTICS DIVISION - SPRINGFIELD, MASS. . POLYVINYL CHLORIDE PRODUCTION.TECHNICAL.SERVICE PROCESS SAFETY AUDIT ^ POLYVINYL CHLORIDE POLYMERIZATION' . July., 1964 /Reported By: A.P. TORRENZANO Date Issued: August 20, 1964 ABSTRACT. This report summarizes the current process safety hazards and a schedule for corrective action. In addition, reference Information was compiled to aid In safe raw material handling procedures and design.. \ RSV0023888 TO: R. A. COFFEY (2) Distribution: A. W. Coaker 0. P. Cohen R. A. Derrah A. G. Erdrnan A. 0. Ericksberg (15) W. F. Gabel (2) R. E., Greenwell C. G. Hallen K. W. Howes N. G. Lieberson E. K. Mahlo D. E. Philpott L. E. Rademacher F. L. Turner W. P. Willis Safety Dept. (2) RSV0023889 INDEX I. INTRODUCTION II.SUMMARY III. RECOMMENDATIONS IV.REFERENCES V. REVIEW OF 1957 PROCESS AUDIT REPORT VI.PROCESSING OF HAZARDOUS RAW MATERIALS a. Vinyl Chloride Monomer b. Vinyl Acetate Monomer c. Tetrahydrofuran d. A-6 e. Diethyl Maleate f. Lauroyl Peroxide g. Aqueous Ammonia h. Sodium Hydroxide i. Calcium Hydroxide j. Other VII. POLYMERIZATION HAZARDS VIII. EMERGENCY PROCEDURES IX.APPENDIX RSV0023890 1. I. INTRODUCTION A process safety audit was initiated at the request of Mr. H. E. Greenwell following a series of process oriented hazards in the Plastics Division during June 1964. The objective of the audit was to Insure proper translation of process technology into safe/ reproducible Manufacturing operations. II. SUMMARY AND CONCLUSIONS The audit was conducted in the following manner in order to detect hazardous operations. A. The 1957 process safety audit report was reviewed. B. The proper procedures for handling the hazardous PVC raw materials were defined and compared to actual plant practices. C. The Tentative Processes were compared to standard operating procedures. D. Discussions were held with supervisors to define polymerization hazards. E. Simpler, faster and more effective emergency procedures were sought. In practically all cases the known technology has been translated into safe equipment design and up-to-date operating procedures. The areas requiring further decisions and/or improvements have been listed in Section III of this report. In summary, the audit showed that numerous safety improve ments have been effected during the past seven years; one of the most important has been the introduction of styrene short-stop agent. Naturally VCM continues to be the major potential hazard in the area; new potential hazards intro duced recently are; THF, A-6 catalyst, DEM and NH^OH. Raw material handling has.been monitored closely but some additional safeguards are necessary, as described in Section III. The two most probable significant hazards in the polymerization area have been active PTS projects; the accidental dumping of the wrong kettle; the spontaneous combustion of asbestos saturated with glycerine. RSV0023891 2. Nominal equipment modifications are recommended to the short-stop addition system* emergency Instrument gas supply and kettle jacket Instrument air supply to provide Improved emergency procedures. III. RECOMMENDATIONS Current hazards and recommendations have been summarized in Table 1 together with decision or completion dates for each Items as assigned by Messrs. W. F. Gabel* R. A. Coffey* K. W. Howes and F. T, Molyneux. RSV0023892 TABLE 1 SUMMARY OF PROCESS SAFETY HAZARDS ---------'------------July l$b4---------------- HAZARD COMMENTS ACTION A. Raw Materials 1. Chronic VCM leaks at gasholder during past year. Need permanent solution to stress failures in dome of gasholder. Plant Eng. Proposal: 9/30/64 2. Essentially unrestricted traffic on road south of VCM unloading dock. Review traffic requirements and impose necessary restrictions. Production Implement: 10/1/64 3. No dike protection at; a) 88 Bldg. VCM tanks b) Tank farm pump hose (c) 84 Bldg. VCM tank Problem is compounded further by the inability to isolate area sewer system from remainder of the plant in case of major VCM spill; no disaster communication procedure with north and we3t plants if"VCM sewer"problems should occur. . Production Decision: 10/1/64 4. Potential explosion hazard in copolymer dryer and storage hoppers via diffusion of VAc monomer from product. Extent of problem not fully known; need measurements and reooinmendations to minimize the danger (air spargers, explosion vents, re-inforcement, procedure changes, etc.) P.T.S. Complete Study: 11/15/64 5< Odor of DEM in A-6 dissolving room. Improved housekeeping program necessary. Production - 9/15/64 6. Erroneous use of DAM for DEM in A-6 dissolving. a. Highlight DEM drums b. Study the extent of danger involved in dissolving A-6 in DAM. a. Prod. - 9/15/64 b. FTS - 10/15/64 (Res.) RSV0023893 7. Spillage of L2O2 at the "delayed catalyst bomb" area in 92 Bldg. Further improvement in handling equipment required. Plant Eng. Proposal: 2/I/65 TABLE 1 (Cont'd) HAZARD COMMENTS ACTION 8. Possible spillage of L2O2 or In addition to precautions defined A-6 solution during maintenance in SDP, special supervisory of catalyst charging equipment. attention should be required before the start of any maintenance work on catalyst charging equipment; use of "permit" possible approach. Production - 10/1/64 9. At times, noticeable concen tration of NH3 fumes in operating area during emulsi fier makeup. Improvement in draft system and/ or lower temperature reaction control necessary. Production Proposal; 11/15/64 10= Inadequate facilities for cleanup after NaOH weighing in 84 Bldg, raw material room. Should attempt to replace this hazardous material in the Opalon 440 process with sodium bicarbonate. If not possible. Improve weighing station for NaOH. Production - 9/15/64 11. Lack of protective equipment when handling lime. Operators occasionally fail to use eye protection during lime slurrying operation in 92 Bldg.; re-emphasis of caustic dangers required. Production - 9/15/64 12. Potential danger of set-up batch by using wrong raw material (such as antifoams) for G-l charges. Overall problem of housekeeping, warehouse storage, inventory control. Identification and trans porting .of raw materials to-kettle floor should be reviewed and improvements made. Large volume of antifoams, G-62, glycerine and C-l being handled on 55 gal drum racks; small raw material elevator in 88 Bldg.; lack of space on kettle floor results In no definite location for each raw material. Production Define Program; 11/1/64 RSV0023894 HAZARD 13. Potential danger of set-up batch by using contaminated drum for G-62 packaging TABLE I (Cont *d) COMMENTS Same as Item 12 above ACTION Same as Item 12 B. Polymerization Area 1. Accidental dumping of reacting batch. 2. Spontaneous combustion when asbestos is saturated with glycerine. 3= Corrosion of deglassed^ steel areas In Pfaudler reactors. Active PTS project already under way to provide automatic mechanical safeguard. A safe replacement for glycerine is now being tested using G-62 as the new dura-seal lubricant. Define and start Implementation of a program to upgrade all PVC reactors via nickel plating. PTS Proposed Solution: 11/15/64 PTS Complete Evaluation: 12/1/64 Prod. & Plant Eng. Program: 11/15/64 4. Mischarge or omission of B-l or B-2 causing batch setup, Study and revise the suspending agent charge system to prevent accidental sewering of the charge; greater probability of undetected error now with the closed manhole raw material charging technique. PTS Complete Study: 11/15/64 5= Open dump valve at start of raw material charge sequence leading to VCM leakage. Consider a ''permission switch" to PTS detect or prevent charging of process Proposed water with an open dump valve; Solution: greater probability of undetected error now with the closed manhole raw material charging technique. 11/15/64 RSV0023895 RSV0023896 HAZARD C. Emergency Procedures 1. Imp rovement; Styrene Injection System 2. Improvement : Air Failure Emergency 3,, Improvement: Full Cold Water TABLE 1 (Cont'd) COMMENTS ACTION A styrene short-stop charge system Plant Engineering should be Installed on the step Proposal: 12/1/64 bearing flush line to provide faster, simpler and better protection during any multi-kettle emergency; simul taneous Injection into all kettles can be effected In less than one min. Faster switch-over to an emergency gas supply can be obtained by connecting the newly available plant nitrogen supply line in 88 and 92 Bldg. Into the Instrument air supply manifold; valving and pressure reducer will be necessary. Plant Engineering Proposal: 12/1/64 By Installing a block valve on the instrument air supply valve all jacket water dump valves can be made to "fail-safe" quickly. Plant Engineering Proposal: 12/1/64 NOTE - It would be desirable to install the above features, together with other safety devices at a centralized panel to permit the execution of all emergency operations In a matter of seconds. 3- SOURCES OF INFORMATION 1. Tentative Process, Opalon 9651 and 9661, April 1964 2. Tentative Process, Opalon 740, December 1962 3- Tentative Process, Opalon X-75 -November i960 . 4. Tentative Process, Opalon 440, November, i960. 5* Tentative Process, Opalon X-24, March 1962. 6. Chemical Safety Data Sheets, Mfg. Chemists' Association SD-9 Caustic Soda SD-13 Aqua Ammonia SD"l4 Trichloroethylene SD-31 Acrylonitrile SD-34 Styrene Monomer SD"f?6 Vinyl Chloride SD-75 Vinyl Acetate 7. Status Summary, Fast Catalyst PVC Homopolymer Process, Storage and Handling Phases of. Isopropyl Percarbonate (IPP), 0. W.. Gruebmeyer, L. Vartanian, August 12, 1963* 8. Technical Bulletin 350 - Isopropyl Percarbonate, Pittsburgh. Plate Glass Co,, Chemical Division, 2/23/62. 9. Dangerous Properties of Industrial Materials, N.I. Sax, Reinhold Publishing Co.1963. 10. duPor.t Technical Bulletins, Electrochemicals Department .a. ,Physiological Properties of Tetrahydrofuran Furan Products,, FC2~1060 b. Tetrahydrofuran,.Recommended Handling Procedures Furan Products, FC3-l6i c. Bulk Storage and ..Handling of Tetrahydrofuran Furan Products FCh"^6o 11. Discussions with the following personnel; V. %. Boyen R. H. Cloutman R. A- Derrah W, F. Gabel H. E. Greenwell 0. W. Gruebmeyer 0. G. Hallen D. E. Philpott y. p. Phillips L. E. Rademacher RSV0023897 4. V. REVIEW Off 1957 PROCESS AUDIT The extensive process safety audit performed in 1957 was very helpful to our present audit. Since most of the plant equipment^, basic operating procedures and raw materials have not changed in the past seven years, the potential process hazards listed in 1957 audit were still timely comments. Much has been done to reduce the probability of experiencing a process problem and to minimize the severity of the dangers. Probably the most important safety Improvement since 1957 was the introduction of a short-stop agent. It is now possible to terminate a polymerization within a matter of minutes and thus reduce greatly the dangers of out-of-control batches. For example, a power failure in 1957 could cause 10 to 15 batches to be out-of-control for hours; it is now possible to render all batches to a "dangerless state1' within a short period of time. The 1957 process audit does focus present attention to the VCM storage area where some questionable practices still exist. These and other potential hazards listed in the 1957 were summarized in Table 2, together with comments on current status. RSV0023898 RSV0023899 TA. 1957 PROCESS AUDIT HAZA. 1957 Potential Hazards frNotes A c Raw Material Category .1= Large VCM spillage at tank farm and polymerization constitutes the greatest hazard to the F70 area. <bul d> O rt a .S3, H X 2, Spotting of namerous VCM tank cai s throughout the plant* tank3 ere known to leak VCM. A 3. VCM tanks & lines not properly groundsd. 4. Need sprinkler system over- VCM tank X cars spotted at dock. 5. Yearly Inspection of VCM tanks behind schedule. 6. Need better communication 8c traffic control in the event of an emergency condition. 7. No means for safe emergency vent of X a tank during stack line repairs. 8. Unrestricted motor vehicle traffic south of VCM unloading dock. X 9. VCM thermal expansion cause excessive PRESENT STATUS Comment on Current Status Four additional raw materials of significant potential hazard have been Introduced into FVC area: A-6* THF * DEM & NH40H; however* VCM still presents the greatest disaster hazard to the area. With the newer* larger cars In-preben: service the degree of leakage has been reduced^ however-* the control of number of tanks in the plant- should be reviewed and a practical solution defined. No comment. Make decision and Implement* If necessary. No comment. Disaster control program being updated again by South Plot Safety Council following recentemergency In area. There are additional ramifications to fact that there is only one safe emergency vent system^ should the stack line be down for repairs or out of service due to pluggage or rupture (via an explosion In one building)* the only-other vent point of reactors is Into the kettle room. This problem should be studied further with the consideration of a rooftop vent for secondary relief in the event of stack line failure. This is not a wise practice when tank cars are being unloaded. Area safety council should define and Implement traffic control. Relief device Installed, 10. YCM overflow of gashoId possible via operator error. I T'-1 ao O!o3s X CL) I O' A Although operator error still possible, gas holder level warning system in operation in each area. 11. L>22 s^e<^ overloaded and not properly secured. X New building located in remote area. 12. BzgOo in L-202 drum .introduces a shock sensitive material into the area. X Remote possibility of supplier error. 13= VAc inhibitor level not test X Specification and testing of VAc under good control. 14, Need better communication between Control Lab, Research & Production on control of new raw materials. X Project Board responsibility in the area very well defined. B. Process and Equipment- Category 1. General problems with formulation errors X Now have short-stop agent to reduce the batch control problem; better raw material quality control, esp. VCM, and checks on charging equipment; less sensitive suspension system for homopolymer; quantitative test of PDR-1 charge in copolymer; better SOP and better trained personnel. 2. Power and/or water failure severs hazard. X Use short-stop agent. 3. Emergency procedure for water and instrument air failure not posted. X No comment. 4. Adequacy of stack questionable for major emergency. X Equipment study shows system to be adequate, 5. Inspection of stack lines and knock-out tanks not scheduled adequately. X No comment. RSV0023900 6. Accidental dumping of wrong kettle severe hazard. X Active project to eliminate this possibility via automatic lock of dump valve when kettle pressurized. 7. Agitator speed limitation unknown. X Safe practice in plant. RSV0023901 Dumping of excessive paste latex lumps to sewer. 9- No emergency lighting in 92 Bldg< 10. Copolymer fires in rotary dryer? 11c High volatiles in copolymer and Gpalon 306 a hazard in silos and hoppers. 12. Higher temperatures and pressures in processes reducing safety margin. C. Personnel 1. Insufficient experienced supervisors to handle fully the operation and safety training. X X X X No comment. No comment. Reduced the probability of a fire by mechani cal control of air flow to prevent backdraft or resin onto heatersj possibility of fire still exists. Product volatiles level much lower (2.5/6 down to 1*) nevertheless flammable concentrations may still be possible. This fact, together with the possibility of a fire in copolymer line, constitutes an explosion hazard: A study is required to define the severity of potential hazards and implement corrective measures (air sparging may be entirely adequd In the "Safety Ledger" faster, more complex processes must definitely enter in the debit sidej better technology, more effective safety devices, better training of operators and better procedures are entered in the credit side. Since no quantitive figures are available, the opinion of the author is that a positive balance exists compared to 1957 = Process safety 'follow-up" is an area that merits further attention - X Supervisory and PTS group sufficient and well qualified to.perform the Job. 5- VI. DISCUSSION QN THE PROCESSING OF HAZARDOUS RAW MATERIALS Of the 32 raw materials used In the PVG polymerization area, nine are considered significant potential hazards. The prime hazards associated with each are listed below.. Four of the materials (THF, A-6, DEM and NH40H) are relatively new in the area. Raw Material VCM VAc THF A-6 L2O2 DEM NH40H NaOH. Ca(DH)2 Hazards Stability - X X X Fire & Explosion X X X X X Toxicity or Burns X X X X A. Vinyl Chloride Monomer 1. Introduction Without doubt, the greatest potential hazard in the area is fire and explosion caused by the ignition of VCM spillage. By nature, the PVC area contains over one million pounds of VCM and an explosion could damage the storage equipment and supply more spillage. Any large VCM fire is almost Impossible to extinguish due to the high volatility and low ignition temperature of VCM; fire control is directed at eliminating the source of the VCM spillage and preventing the fire from spreading. Any large VCM spill presents a plant-wide hazard via the sewer system. Most disastrous accidents experienced throughout the world with VCM originated in the reactor room. This year an explosion at a Thompson Chemical Co. plant resulted when a glass Inspection port failed and released thousands of pounds of VCM into the room; equipment failure followed and the VCM vapor was ignited. The ensuing fire and explosion killed seven employees,, RSV0023902 6. A few years ago a plant in Japan was destroyed when a reactor was accidently opened releasing VCM into the area. The same sort of accident occurred in a PVG plant in Italy but fortunately the VCM vapors were not ignited. .An explosion occurred in Springfield many years ago when a tank was overfilled allowing VCM vapors to concentrate in the area^ fortunately, no fatalities resulted. VCM leakage in the polymerization can be caused by (l) uncontrolled reactions, (2) equipment failure, and (3) operational error. All three cases were studied during this audit and recommendations made in the appropriate sections of this report. 2. Physical and Chemical Properties Molecular Weight .......... Critical Pressure .... Critical Temperature . Boiling Point ................. Color .' .............. Odor ................. .. Physical State ....... Freezing Point ....... Specific Gravity ...., Vapor Density ................. Vapor Pressure .............. Flash Point .......... Explosive Limits ..,.. 62.5 52.7 atm. 158.4C (31TF) -13.8C (+7F). Colorless or water-white Sweet smelling gas Gas at ordinary temperature and pressure -- Liquid under pressure in cylinders or pressure vessels at room temperature. -153-7C (-245F) .9121 at 20/20- 2,15 (air = 1.0) 2580mm of mercury at 20C -78C (-108.4F). Open-Cup Lower Upper.22$, by volume in air. 3. Hazardous Properties (Summary) a. Health Hazard Aside from the risk of fire and explosion, vinyl chloride presents no other serious problem in general handling. The threshold limit value is 500 ppm. In concentrations well above 500 ppm vinyl chloride acts as a mild general anesthetic. In contact with the skin vinyl chloride is irritating. Prolonged contact will result in refrigeration and freezing. b. Fire Hazard Vinyl chloride vapors form flammable mixtures with air at all temperatures above -78C. Fires involving large quantities of liquid are almost impossible to extinguish^ it is usually RSV0023903 necessary to stop the source of VCM leakage. 4. Key Points for Safe Handling 7- a. Keep away from heat,, sparks and open flame. b. Electrical, equipment should conform to the National Electrical Code,, Class I* Division II for storage and Class I, Division I for use. c. Provide adequate ventilation. d. Ground equipment and containers before discharging to reduce danger of ignition from static 3parks; resistance to ground should never exceed 25 ohms. e. In discharging^ do not heat containers above 50C. No heat should be applied to tank cars. f. All equipment should be steel and have a designed working pressure of at least 100-150 psi; no copper or silver allowed^ no glass equipment such as rotameter and sight glasses allowed, g. Storage tanks should be protected with a water spray system. Adequate diking should be provided under tank area in case of vessel rupture. For spill control,, all openings in sewer system 1 should be trapped for segregation and extlnguisftnent. h. Do not enter spillage area without proper respira tory protection. 1. Chemical safety goggles should be worn when discharging containers or tank cars or sample taking. . j. Frequent inspections of equipment and vessels containing vinyl chloride should be made to detect or prevent leaks. Note chat vinyl chloride is generally non-corrosive at normal atmospheric cemperacures when dry ;moisture-free),, However, mild to appreciable corrosion has been notedj this may be due to the presence of impurities. In contact with water at elevated temperatures, vinyl chloride accelerates corrosion of iron or steel. RSV0023904 8. 5- Specific Hazards with VCM Storage & Handling at Springfield (a) Recovered VCM gasholder leaks have been a chronic _ . problem during the last year. Solutions Permanent upgrading of facilities required. (b) Vehicle traffic on the road Immediately south of tank farm essentially unrestricted. Solution; Review traffic requirements In this area -- eliminate or reduce (c) No dike protection in the following locations: _ ,, (l) "washed" VCM tanks west of 88 Bldg.. (2) tank farm.pump house, (3) VCM tank east of 84 Bldg. Problem is further compounded by Inability to isolate sewer system in area from remainder of plant. In addition, there is no forma3. procedure for communica tions with other sections of the plant in the event of large VCM spillage. Solution: Request study of the situation by area safety council. (d) Recommendation: Once per year, the area monthly ,, . safety program, should be directed at: (1) Meeting - "Safety In Handling VCM", covering . . the proper.techniques for VCM transfer and sampling, fire and health hazards, protective equipment and emergency procedures for VCM spillage and/or VCM fire. Personnel should Include Production, V & M and Maintenance.2 (2) Report - condition of present VCM storage and . handling equipment^ condition of safety equipment. 6. Specific Hazards with VCM in Polymerization Area See Section VII, "Polymerization Hazards". RSV0023905 9- B. Vinyl Acetate Monomer 1. Introduction Vinyl acecate has been employed for many years in the production of Opalon 500 series copolymers. During the last two years VAc monomer has been supplied solely by Texas City to the Springfield operation. Improved storage and handling equipment have been Installed during the years and better raw material quality control has been defined. No significant accidents have been experienced with VAc during the storage and handling of this material. In the polymerisation area,, the dangers of this material are "'covered1' by the more difficult co-monomer, vinyl chloride. It should be noted that the copolymer polymerization suspension system Is sensitive to raw material Impurities and operating conditions. Out-of control polymerisations usually result in rapid fusion of the slurry particles and the reaction mass behaves more like a polymer melt than a suspension. As a result,, pluggage of the emergency vent system may occur and the ensuing high pressure buildup can cause serious equipment damage with VGM and VAc leakage. The presence of occluded monomers In the copolymer particles presents a potential hazard in the drying sind storage of the product. Explosive concentrations are possible by the diffusion of these monomers into the air space above the product. Experience has shown that heat degraded copolymer can be ignited by contact with air temperatures in the 120-160G range.2 2. Physical ana Chemical Properties Molecular Weight Physical State ,,... t . . Critical Temperature Critical Pressure o o Freezing Point ,,,, Odor Bolling Point .......... Vapor Density Specific Gravity ....... Solubility In Water @ 20 G Flash Point ............ Explosive Limits ....... Ll o o 86.1 Liquid at ordinary temp. and pressure5 clear and colorless 228.9C (444F) 22.4 atm. 100C (-148F) Not unpleasant, sweetish snle.ll in small quantities 72.7C (163F) 2.97 (air = 1.0) 0.9338 (water =.1,0) 1.98 wt,,j6 "55C (22F) Open cup Lower 2.6#j Upper 13.4# by volume in air RSV0023906 10. 3* Hazardous Properties (a) Health Hazards -- No known Important health hazards; it is not an active Irritant locally and no systemic or chronic effects have been recorded. (b) Fire Hazards -- Forms flammable and explosive mixtures with air at temperatures of 22 F and above. 4. Key Points for Safe Handling VAc Monomer . (a) Keep away from heac, sparks and open flame. (b) Electrical equipment should conform to the National Electrical Code Class I, Division XX for storage, and Class I, Division I for use. (c) Provide adequate ventilation,, (d) Ground equipment and containers before discharging to reduce danger of Ignition from static sparks. (e) Totally enclosed systems should be used for . processing vinyl acetate as a raw material. (f) Must be inhibited with dlphenylamine to prevent polymerization in storage equipment and subsequent temperature rise. (g) Explosion vents should oe used to reduce destructive damage to duets, mixers, blenderss dryers and similar equipment in which flammable vapors are liable to concentr; vow o (h) Chemical goggles anu gloves should be worn when taking samples,,(i) (i) Frequent inspection of equipment and vessels containing vinyl acetate should be made to detect or prevent leaks,, Special precautions listed In Data Sheet Sp .75 should be followed in preparing equipment for personnel entry. 5. Specific Hazards at Springfield 1. See Section VXI, "'Polymerization Hazards". 2. Although copolymer fire hazards in the rotary dryer have been reduced by recent Installation of a "danper and blower", tne possibility of an explosion in the dryer,, hoppers, silos and bulk cars should be studied. RSV0023907 C. Tetrahydrofuran (THP) 11. 1. Introduction THF has been in limited use in the PVC area for approximately three years and until recently employed to solvent clean only four reactors. A new solvent cleaning process is now being started up for extensive use in both 88 Bldg, and 92 Bldg. Quantities up to 15,000 gallons will be stored in the area. Facilities have, been installed to solvent ^lean three reactors per day and to distill approx. 6,000 gallons of PVC ladened THF, to remove the PVC. The only incident experienced at Springfield to date with THF was a feeling of nausea and dizziness by an instrument man while repairing a gaiigej during this operation, the man was exposed to excessive concen trations of THF vapor emitting from an open valve on the storage tank. 2. Physical and Chemical Properties Odor .4O..0....OOD..0... Ethereal Color .................. Clear, colorless liquid Molecular Weight ....... 72.10 Bolling Point (1 atm)___ 66C (151F) Freezing Point____ ...... -108.5C (-163F) Specific Gravity, 20/4C 0.888- Welght, #/gal. at 20C.. 7.4 Flash Point (tag closed _cup)....... -14.5C (6F) Flammability Limits, $ .by vol. in air at 25C, 2.0 lowerj 11.8 upper Ignition Temperature.... 32lC (6l0F) Miscibilityi water? esters . ....... infinite acetones; alcohols; chlorinated hydrocarbons 3. Hazardous Properties (a) Health Hazard Considered a toxic material with a threshold limit value of 200 ppm; odor readily detected at 50 ppm. Excessive exposure may cause nausea, dizziness and headache; symptoms disappear quickly on access to fresh air. RSV0023908 THF does not sensitize the skin or cause irritation beyond the normal defatting action of organic solvents. THF should never be taken internally. Contact with the eyes should be avoided via protective equipment. (b) Fire Hazard 12. THF .Is about as flammable as acetone and gasoline. Unst.abiu.lzed THF forms an organic peroxide when exposed to air; . violent decomposition can occur if the peroxide is accumulated. 4. Key Points for Safe Handling a. THF storage must be stabilized with .025$ butylated hydroxytoluene s BHT., (or 0.10$ hydroquinone) to prevent peroxide.formation. Samples should be tested regularly to monitor the peroxide levsuj must be maintained below 0.10$ peroxide. Records should be maintained to help monitor the system peroxide level. b. THF should be maintained on the basic side to (1) prevent decomposition and THF-peroxlde formation and (2) prevent corrosion of steel equipment ,, c. Bulk transfer of THF from tank truck to storage equipment must follow regulations for"flammable liquid" handling. (1) performed only by qualified personnel. (.2': Transfer only in daylight. (3, Motor snut-off during unloading. (4) Use only non-sparking tools. Electrical ground all tanks and lines. '<.6, Etecr.deal facilities must comply with NEC for Glass 7,D Hazardous Location. Operator must oe present during entire transfer operation. (8; Unloading connections must be removed promptly after' completion of the transfer. d. All storage tanks., pumps and piping should be electcally grounded to discharge static electricity. e. All s'orage tanks must be protected to prevent excessive pressure or vacuum buildup as solvent is transferred. A safety vent should be used on all relief lines. f. Welded pipe connections are preferred because ordinary pipe dopes quickly leach out and leaks develop at fittings. RSV0023909 g. Only recommended materials should be used for gas.tcet.s and seals3 see dupont Bulletin "Furan Products" FC 5-260. h. All THF leaks must be isolated and stopped immediately. Tne area should be flushed with water and adequate ventilation provided to prevent toxic concentrations from accumulating. In short, handling of THF must be odorless. 13- 1. THF must, be kept away from heat. ,, sparks and open flames. j . All electrical handling equipment must conform to National Electrical Code Class I. k. Design must eliminate any pits or Isolated areas where adequate ventilation is not provided. l. Chemical safety gogii.v'i and gloves must be worn when sampling repairing equipment, discharging containers or when there is danger of leaks or splashes ,, m. Air must be excluded from all tanks and reactors when discharging THF into the vessel with sufficient velocity.to buildup a static charge -- le,,, rinsing kettle with THF via spray nozzles. n. All equipment including storage tankss recovery tank;., pipe lines and condensers^ should be Inspected regularly to Insure integrity of design. No temporary facilities,, such as flexible lines, hoses, etc. should be substituted for designed equipment. o The danger of trapped THF in kettle-reflux condensers should be recognized before entry into the equipment. 5- Specific Hazards at Springfield The potential hazards associated with THF handling are fully recognized by one "Start-up Team" presently engaged in snaking down the equipment installation and demonstrating the "hoirent Cleaning Process". No further comments are necessary xn this audit. RSV0023910 14. D. Isopropyl Percarbonate (A-6) 1. Introduction The A~6 catalyst has teen employed routinely since April 1964 for the production of suspension homo polymer resins in 88 Bldg. This catalyst was a replacement for lauroyl peroxide, which is still used in 92 Bldg, suspension polymerization. The basic flow of A-6 material through the plant is as follows % (a) A-6 crystalline solid is stored in the remote catalyst area on the hill; the material Is packed in 10 lb. stainless steel trays; the trays are maintained In contact with dry ice In the original shipping container, an Insulated box. (b) Dally requirements are transferred from the primary storage to the area Storage room. (c) A-6 crystalline solid is dissolved in approxi mately a Is3 ratio with diethyl maleate (DEM). (d) A-6 solution is transported from the storage_ (and dissolving) room to the kettle floor. (e) A-6 solution is,transferred to a refrigerated charge tank located at each kettle; quantity of solution is approximately 1 gallon. (f) The A-6 solution Is pressurized with nitrogen and forced into the reactor at the appropriate time in the polymerization cycle. The crystalline A-6 is unstable at temperatures above 8C, the melting point. If stored at room temperature the material will decompose violently, releasing flammable and explosive gases. The A-6 solution Is much more stable and temperatures in excess of 50C are required to attain the autodecomposition point for the quantity usually handled; violent decomposition will occur at temperatures above 85C with the expanding gases capable of rupturing a 4,000 psl pressure vessel. With a 2" diameter vent for the holding vessel, the decompo sition gases release to the atmosphere without any appreciable pressure developments. In the brief 4-month period since starting the commercial usage of A-6 catalyst, no hazardous incidents have occurred, except for one when the cover to the primary storage box was lifted by excessive winds one evening. When noted the following day, about half of the dry ice refrigerant had sub limed. Since then, monitoring equipment has been Installed and changes in design effected to prevent a similar situation. RSV0023911 15- For safety purposes, it is mandatory that the regulations, procedures and equipment be utilized properly. Close follow-up is always necessary to avoid complacency and utilization of faulty equip ment . The hazards with A-6 solid, DEM and A-6 solution are defined separately in the sectionsfollowing. 2. Physical and Chemical Properties of A-6 Solid Physical State . ,, .,,. .... Colorless, crystalline solid below +8C Molecular Weight ....... 206 Melting Point .......... 8 to 10C Specific Gravity ....... 1.080 (water = 1.0) Solubility in water @25 C .04$, Solubility in organic SolventsMiscible with aliphatic and aromatic hydrocarbon esters, ethers, chlorinated hydro carbons Heat of Fusion ......... 25 BTU/lb. Active oxygen content... 7<>8$ Stability. A-6 is highly unstable at ambient conditions; material melts at 8 to 10C, autodecomposition occurs at 14-18C and materials rapidly reach temperatures of 85C at which point sudden effervescence occurs producing flammable products Including Isopropyl alcohol, acetone, acetaldehyde, and ethane. Close by sources of ignition constitute an explosion hazard, while complete confinement of the decomposing product can lead to vessel rupture and/or explosion. Reactivity.............. A-6 spontaneously decomposes on contact with mineral acids. Decomposition is accelerated in the presence of amines, aqueous potassium hydroxide or other strong gases. Friction and Shock ..... Sensitive, but many times less sensitive than benzoyl peroxide. Unusual conditions of heat, friction or shock should be avoided. 3. Hazardous Properties of A-6 Solid (a) Health Hazard Material is considered to be slightly toxic. Skin contact with A-6 will cause local damage to the tissue because of the oxidizing power and the low temperature of the material. RSV0023912 (b) Fire & Explosion Hazard 16. Dangerous if material is permitted to decompose; the decomposition products are flammable and explosive. Key Points for Safe Handling of A-6 Solid a. Primary storage of A-6 must be in an isolated area; local insurance Inspection bureau and fire authorities should be consulted concerning location -- distance from highways, buildings, tc. b. Storage area must be secured from trespassers. c. The storage facilities must be adequately vented to remove CO2 gases evolved by sublimation of the dry ice refrigerant; a partially opened shed with good wind protection is recommended. d. The stainless trays in which the A-6 is packed must always be in contact with dry ice; dally inspection and good lhventory of dry ice is mandatory. e. A warning system - such as a flashing red light - is recommended to monitor the dally Inspection and the accidental failure to replace the cover of the Insulated A-6 storage box, thus causing rapid loss of dry ice. f. Only minimum amounts of A-6 Should be stored in the polymerization area; the storage facilities in the polymerization area should be a concrete room designed to contain any explosion and direct deconposition gases to the outside of the building. g. The storage facilities must be well ventilated and not contain any form of heat such as steam or hot water pipes, radiators and light bulbs. Naturally all open flames and spark producing tools must be omitted from this area. h. The storage areas should not contain any.electrical equipment; all moving equipment must be air operated. I. The A-6 catalyst should not be subjected to any frictional or grinding operation. J. The "transport boxes", used to carry the small dally A-6 requirements from the primary storage area to the plant storage room, must always be accounted for and never left outside the plant storage room -- (which is normally called the "dissolving room.). RSV0023913 17- It. The plant storage room must never be used for any purpose other than that Intended; good housekeeping is essential to safe handling. l. A-6 crystalline solid should not be elevated more than 7 feet off the ground. m. A-6 spills must be cleaned up Immediately. Large spills should be swept up (use fox tall brush) with Vermlcullte, placed In tray containing dry ice and disposed of by spreading it over a sandy area in a safe area. Small spills should be washed up with soap and water. 5* Specific Hazards at Springfield None RSV0023914 18. E. Diethyl Maleate (DEM) 1. Introduction This material was Introduced into the PVC area to serve as a solvent for the A-6 since it is the solution form which makes it practical to charge the A-6 catalyst under precisely controlled condition to the batch reactor. DEM was selected from tests on series of solvents based on solubility, stability, non-corrosiveness, low toxicity, flammability and the fact that DEM copolymerizes in vinyl chloride reactions thus minimizing undeslreable solvent side effects. The principle hazard with this material is handling; material is a skin sensitizer of moderate to high potency. Three operators have experienced skin rashes while handling this material, requiring 3 to 7 days to clear the local irritation. Since providing better ventilation and enforcing better hygenlc rules for handling, no further incidents have occurred. 2. Chemical and Physical Properties Odor ...................................... Noticeable Color ................................... Colorless, mobile liquid at ambient conditions Molecular Weight............ 172.2 Boiling Point ........ 225 C Freezing Point .............. -UC Flash Point ..................... 93C (open cup) Solubility in Water... Slight Vapor Pressure @20C.. 0.07 mm Hg. Density at 20C.............. 8.9 lbs./gal. Vapor Density(air=1.0) 5*93 3 * Hazardous Properties (a) Health Hazard .... Slightly toxic material with . . the prime hazard of being a moderate to highly potent skin sensitizer, (b) Fire Hazard ............ Only a moderate fire hazard due _ - to low vapor pressure and high flash point RSV0023915 4. Key Points for Safe Handling 19- a. Use material only In well ventilated areas; forced air circulation necessary due to high vapor density,, b. Use chemical goggles (or fire shield) and "oil and chemical resistant" gloves whenever handling this material. c. In case of accidental spillage on body, remove clothes and wash skin with soap and water. The exposed eye should be flushed for at least 15 minutes with water followed by Immediate medical attention. d. Floor spillage should be washed down promptly with water. e. Acid impurities in DEM causes attack of steel and brass handling equipment and causes a more disagreeable solvent odor; adherence to^quallty specification is required. 5. Specific Hazards at Springfield a- Closer attention to housekeeping In the dissolving room is necessary to prevent odor In room from reaching a disagreeable level. Solution; Weekly scrubbing of room should be implemented, together with close monitoring of the dally housekeeping. D. and E. A-6 Solution 1. Introduction The A-6/DEM solution greatly diminishes the stability problem of the catalyst; however, considerable potential hazards still exist. Decomposition, fire and ejqjlosion are still possible. 2. Physical and Chemical Properties Odor ......... Color .oo... Boiling Point Freezing Point Heat of Fusion ...... Same as DEM Colorless, mobile liquid above 0C Decomposes Depends on solution concentration; -35C for 40$ solution 25 BTU/lb. RSV0023916 Stability 20. Tests have shown that decreasing the A-6 solution concentration increases the stability of the system. A 50$ solution is maximum allowable based on solution shock sensitivity and difficulty in obtaining further A-6 dissolution, A 40-50$ solution flowed the following storage stability. Temperature Time Stability -10 C - 3C +15 C +4qq 4 moSo Lost 4$ activity in 4 months 2 mos. No detectable change 1 moo Lost 2$ activity in one week 1 gallon, of material was raised to 40C in a 4-gallon pressure vesselj tempera ture slowly climbed over l4 hours starting to accelerate at 48C. From 48C the decomposition progressed, rapidly with a violet decomposition at 80+G ,, The 28-30$ solution routinely used in plant operation is stored at 0 to 5*0,5 at 10C an alarm system 1b activated and at 20G the material is disposed thus precluding any further problems, 3. Hazardous Properties (a) Health Hazard -- The solution 1b considered to be . - slightly toxic and a highly potent skin sensitizer. (b) Fire Hazard -_ -- Instability of the solution to temperatures above 20C is the principle hazard. Material is considered ''thermally shock sensitive".. Decomposition products are highly flammable. 4. Key Points to Safe .Handling a. Only stainless steel equipment should be used to dissolve A-6j metal contamination can reduce the stability of the solution. b. Only the specifically designed dissolving tank should be used for solution make-up. c. Be sure other drum liquids are not used erroneously in place of DEM5 possible error is DAM or antifoams. d. Never exceed a 40$ weight solution of A-6 in DEM. RSV0023917 21. e. Posted steps for dissolution operation must be followed to avoid spillage or overcharging. f. Spills should be soaked up Immediately with Vermiculite and taken to a disposal area; the floor should be washed down with water. g. The disposal area should be a sandy area, restricted to traffic. Gradual decomposition will occur. h. The following operating Instructions should be posted in the "Dissolving Room". l) Wear goggles and gloves. 2 j Check dry ice level in all storage boxes. I3) Close dissolving tank drain valve. 4) Check current batch formulation data. 5} Tare weigh dissolving tank. 6j Charge DEM to dissolving tank. 7; Tare scale again; check scale accuracy once _ , per shift. (8) Add A-6 carefully - avoid spillage. (9) Carefully move dissolving tank to agitator . ,, station. (10) Slowly lower agitator into tank and.dissolve A-6. (ll) During 10-minute dissolvlngperlod, operator should log all pertinent data on batch sheet. (12) Stop agitator, raise slowly. 13} Close dissolving tank cover after mixing; wing nut should be threaded down completely. (14) Immediately transport tank to kettle floor; . transfer A-6 solution to correct kettle hold tank. (15) Do not leave A-6 dissolving area until operation _ is completed. i. The A-6 kettle hold tank must be vented at all times except for the brief 5 minutes when the tank is pressurized to charge A-6 solution into the kettle. The 8 inch diameter, two gallon hold tank must be equipped with a full 2 inch vent line extending above the roof line. A fail-safe valve should be installed to automatically open the vent line after an eight-minute period, should the valve be left closed after the charging operation. j. The A-6 kettle hold tank must be refrigerated; maintain A-6 solution below 5C. k. The following operating Instructions should beRSV0023918 posted at the A-6 solution charge panel. 22. 1) Wear goggles and gloves. 2i Place dissolving tank in the support ring. 3j Loosen cover of the dissolving tank. 14i Be sure vent valve is open. 5J Drain any liquid from the hold tank. 6j Check brine temperature. 7) Check that bottom valves on hold tanks are _ _ closed. (8) Gravity transfer the A-6 solution When batch temperature is at desired range for A-6 charging, (a) drop JTRC set point to 45 C (b) pressurize hold tank. r (10) Inject.the A-6 solution into the kettle; . close drain valve when tank pressure drops to 150 psig. (11) After the injection, depressurize the hold 1. The,, ftoalnlokw. ing emergency procedure should be (1p2o)steDdraaint hthoeld At-a6nks.olution control panel. (13) Adjust water flush rate to 6 gph. (1) Normal A-6 solution Temperature 0 to 5C (2) Warning temperature (via alarm ,, ,, system) 10C (3) Drain A-6 solution into container lS^C _ ,, with Vermicullte and dry ice (4) Allow A-6 solution to decompose in 30C or - - hold tank with 2" vent valve open higher m. Under no conditions should temporary or other equipment be used to charge A-6 into the kettle. 5. Specific Hazards to Springfield None RSV0023919 F. Lauroyl Peroxide 23- 1. Introduction This peroxide has been used in suspension polymeriza tion since the initial plant installation. Recently, A~6 catalyst has replaced the lauroyl peroxide in 88 Bldg. operationj the lauroyl peroxide is now used in one. building only. The handling procedure for this material consists of the followings a. Prime storage of 100 lb, drums in separate remote building. b. Transport of 4 to 8 drums of catalyst daily to the operating area. c. Transporting one drum of catalyst at a time to the kettle floor weigh station. d. Weighing out batch charge, 20 to 45 lbs., in a carrying pall. e. Loading the "delayed catalyst bomb" charge equipment. f. Flushing the solid catalyst into the kettle at the correct time in the polymerization cycle. About a year and a half ago a flash fire was experienced when a small amount of peroxide spilled onto hot pipes below the kettle floor grating. The flame startled the operator who in turn dropped the carrying pall causing the remaining catalyst to spill and catch fire. No injuries or damages resulted. The cause of the fire was believed to be autoignition of the decomposition gases of lauroyl peroxide. It was estimated, based on laboratory trials, that a 10-15 foot flame could be produced with 25 grams of catalyst. Hence, even very minute spills of catalyst can be dangerous. 2. Physical and Chemical Properties Formula. o 4 a 0 0 Molecular Weight Appearance 0 0 4 0 0 Odor 4 0 4 0 4 04 0 0 Taste 0 0 0 4 0 0 0 4} Melting Point (CllH23C0)202 398.6 Soft, white granules Faint None O 49-53C RSV0023920 24. Solubility (20C) Very Soluble ........ (more,than 30 grams)* Benzene, Carbon Disulfide, Carbon Tetrachloride, Toluene, Chloro- benzene. Chloroform, Ethylene Dichloride, Trichloroethylene Soluble (10-30 grams)* Acetone, Benzaldehyde, Butyl Acetate, Ethyl Acetate, Methyl Ethyl Ketone Fairly Soluble ...... Benzyl Acetate, Diethyl Phthalate, (3 to 10 grams)* Kerosene Slightly Soluble..... (0,1 to 3 grams)* Benzyl Benzoate, n-Butyl Alcohol, Dlbutyl Phthalate, Ethyl Alcohol, Iso-Amyl Alcohol, Methyl Alcohol Insoluble............ Water (less than 0.1 grams)* *per 100 grams of solvent Stability Time, Weeks J6 Loss of Peroxide Content 2C (35.6F) 30C (86F) 40C (104F) 4 6.1 o`i 4.4 8 0.2 0.6 8.1 13 0.7 1.1 27.5 26 1.2 1.6 90.8 39 1.5 2.2 96.6 5 2 1.5 3.5 -- Half Life Data of L202 in Benzene (0.2 moles per liter of .solvent) E, Activation Energy, k cal per mole .... 30.4 Temperature Half Life 30 C 40 5 60 70 80 90 115 900 hrs. 220 54 3 0.8 0.2 1.0 minutes RSV0023921 25. 3. Hazardous Properties (a) Health Hazard -- Although it can cause slight _,,. skin and -eye irritation, the material presents no significant health hazard. (b) Fire Hazard -- - -- The material can be stored safely at room temperature; at elevated temperatures the material is ''thermally shock sensitive" with violent decomposition or even explosion occurring. Although the decomposition products are extremely flammable, the solid burns similar to wax with a soft flame. 4. Key Points to Safe Handling a. Material storage must conform to safe practices for peroxide storage; insurance and fire conqpanies 7 should be consulted when designing, the equipment. b. Keep away from all heat producing equipment: hot pipes, light bulbs, electrical equipment, open flaiiies or sparking tools. S. The amount of peroxide in the processing area should be limited to the minimum dally processing requirements. d* The containers of peroxide should be stacked in such a way that the water from the sprinkler system will reach and wet them in case of fire. e. The peroxide should be stored in the same containers used by the manufacturers for shipping the material. f. If the shipping drum is to be re-used for any plant purpose (such as trash collection) extreme care must be used in completely cleaning out any residual peroxide granulars in the drum. g. The peroxide should not be subjected to any frictional or grinding operation. h. The peroxide should not be added to materials at tenperatures exceeding safe tolerances. I. Lauroyl peroxide should always be handled in clean, properly designed equipment. J. Spills should be removed immediately; the floor area should be washed down completely to remove, even trace residues. RSV0023922 26. k. The performance of maintenance and repair work on peroxide handling equipment should require a "permit" from supervisory personnel. l. Good housekeeping and maintenance of the plant facilities and equipment are essential in all storage and processing areas. A program should he established to accomplish these objectives. m. Plant personnel should be thoroughly trained in the emergency procedures required for fires, explosions or accidental spillage. (1) If a fire occurs in the peroxide storage area, _ _ the automatic extinguishing system should be allowed to take over and all personnel should leave. Do not approach the fire or attempt to use first aid fire extinguisher) an explosion is a possibility. Use a water spray from a safe distance. (2) Should a fire occur in the vicinity of the , peroxide storage area, maintain a cooling water spray over the outside of the containers to guard against overheating. (3) Glean up operations after a fire should r\ot be _ ,, attempted until all of the peroxide has cooled down completely. 5. Specific Hazards a. Spillage of small quantities of lauroyl peroxide is still evident at both the weighing station and at the "delayed catalyst bomb" area. Improved handling methods should be considered and Implemented. (b) The maintenance of both L2O2 and A-6 handling . . equipment should receive special supervisory attention to avoid spillage. Action to implement this needs definition. RSV0023923 27. G. Aqua Ammonia 1. Introduction Ammonium hydroxide is used solely in the emulsion polymerization Opalon 440 process. The material is reacted with lauric acid to form an emulsifier, ammonium laurate. The reaction takes place in a 200 gallon tank from which the solution is pumped into the kettle before and during the polymerization cycle. 2. Chemical and Physical Properties Grades and Strengths Grade A - 29.4$ NH3 Grade B - 25# - NH3 Grade C - 1556 NH3 USP - 27-29$ NHo CP - 28$ NH3 Color: Liquid - colorless Gas - colorless Odors Pungent Densitys O.8974 (26Be) for 29.4$ NH3 at 15.5C Corrosives To copper, copper alloys, aluminum alloys and galvanized surfaces. Affinity for Waters NH3 gas is very soluble. Light Sensitives No* Explosive Limits of NH3 Gass 16 to 25$ by volume in air. Ignition Temp of NH3 Gass 651C (1204F) Melting point of 29.4$ NH3s -72.4C (-98F) Vapor Pressure of Aqua Ammonias $ NH^.Wt. 32F 10 0.6 15 1.1 20 1.7 25 2.8 30 4.6 40 11.2 50 F Pressure, psia 80 F 100 F 120F i4o: 1.1 1.8 2.7 4.8 ____7 .4 J |1 17.2 2.5 4.2 3-9 6.3 6.0 1 9*7 9.9 _pC5T6 15.2 23.1 32.7 48.4 6.7 10.1 I l4?]*88 J 14,9 22.2 23.O 34.0 34.5 50.3 69.5 97-1 RSV0023924 29- Gaseous Cone, Effects on Unprotected Exposure Period ppm Worker 400 Causes Irritation of Ordinary not serious throat for short exposure 700 Causes Irritation of Ordinary not serious eyes for short exposure 1720 Causes convulsive coughing No exposure permlssablej may be fatal after short exposure 5,000-10,000 Causes respiratory spasm, strangulation, asphyxia No exposure permissable (rapidly fatal) (g) Safety showers and eye bubblers should be immediately available at unloading stations and operating areas. (h) Protective clothing must be worn when handling, sampling or repairing equipment. Eye protection is a must. (i) Operators should be trained not only in operating procedures but also specific first aid action for (l) inhalation,(2)contact with skin and mucous membrane and (3) contact with eyes. (j) Contact with eyes, even in minute quantities, is dangerous. Eyes should be irrigated immediately and copiously with water for a minimum of 15 minutes. The eyelid should be held apart during the irrigation to insure contact of water. A physician should be called immediately. 5. Specific Hazards at Springfield The draft system above the emulsifier tank is marginal; at times NH3 fumes in the room are detectable and irritating. This problem Is compounded by the effect of solution temperatures on the rate of NH3 vapor generation. The operation should be improved to prevent uncomfortable concentrations of NHj. RSV0023926 30. H. Sodium Hydroxide 1. Introduction This material Is used In only limited quantities In the emulsion polymerization Opalon 440 process. A weak solution, approx. 0.25$, is made by adding flake caustic to water. The liquid caustic soda is pumped Into the reactor to stabilize the latex. No accidents or hazardous incidents have been experienced to date with this operation. 2. Physical and Chemical Properties a. Anhydrous Form Color........... Boiling Point .. Melting Point .. Corrosive.............. Dangerous Reaction.., Hydroscopic................. Deliquescent ............ White or light gray White heat 310-320C (590-6o8F) Non corrosive to rubber at atmospheric conditions. Slowly corrosive to iron, copper and Monel metal. Destroys living tissue. Yes. Considerable heat is generated when water is added to caustic soda; boiling and spattering of hot caustic solution may result. Yes Yes b. Liquid Caustic Soda Color ................................. Water white; occasionally gray 50$ Solution 73$ Solution Boiling Point (760 min) Crystallization ,, Solidification 142 to 148C +12 to +15C +5C 188 to 198C +63C +62C Flash Point.......... None Ignition Tenp............ None; not combustible 3. Hazardous Properties a. Health Hazard Caustic soda is a strong alkali and can cause severe burns. Contact with the eyes, either in solid form or in solution can cause permanent damage. RSV0023927 31. b. Fire Hazard - None 4. Key Points to Safe Handling a. Wherever caustic soda is stored, unloaded, handled, or used, abundant water should be available for emergency use in dissolving and flushing away spilled caustic. b. Safety shower and eye bubbler should be located in every area where caustic soda is handled. c. Protective clothing must be worn by all operators handling or working near caustic soda. (l) close fitting industrial goggles l 2J rubber gloves (3; rubber apron d. Operators should be trained for specific first aid action for skin and eyes contact with caustic soda. 5 Specific Hazards Consideration should be given to substituting a sodium salt for the presently .used sodium hydroxide in Opalon 440 process; this would eliminate the handling of this hazardous material. Should substitution not be possible then Improved handling and weighing facilities will be needed; it is not possible to wash down spills in the present storage-weighing room. - RSV0023928 32. I. Calcium Hydroxide 1. Introduction Lime Is slurried in water and charged as an antifoam to copolymer suspension processes. The normal quantities involved are 30 lbs. of lime added to 10 gallons of water. This operation has been in existence for approx. 3 years without any hazardous incidents. 2. Physical and Chemical Properties a. Lime, GaO Molecular Weight ,.... 56 Appearance ...o..coo Cubic, colorless crystals In a finely ground state Melting Point ....... 2580C Bolling point . . . . . . . 2850C Reactive............. Upon exposure to dampness or water, it for calcium hydroxide. Heat is liberated during the reaction. b. Hydrated Llmej Ca(0H)2 Molecular Weight .... 74.1 Melting Point ....... -H2O at 580C Bolling Point ....... Decomposes Density ............. 2.343 3. Hazardous Properties a. Health Material has a caustic reaction and therefore is irritating to the eyes, skin and respiratory system. b. Fire - none 4, Key Points to Safe Handling a. Equipment should be designed to minimize spilling and splattering hazards. b. Protective equipment must be worn whenever handling lime or hydrated lime. Minimum equipment consists of safety goggles and rubber gloves. Aprons and rubber boots should be worn If spills or splashing dangers exist. RSV0023929 33. c,, A dust respirator should be used when necessary to prevent inhalation of lime dust,, 5. Specific Hazards Use of protective eye equipment has not been faithfully observed by all operators; additional emphasis on lime protection Is needed In this operation. RSV0023930 J. OTHERS 34. 1. Trichloroethylene (TCE) a. TCE is toxic by Inhalation; high concentrations cause narcosis and anesthesia; threshold limit value is 200 ppm. b. At high temperatures, TCE decomposes to highly toxic materials (phosgene). c. Strong alkalies may react with TCE to form explosive mlsture (dichloracetylene). Good ventilation and protective equipment is required to safely handle TCE; design of plant equipment should avoid the-possibility of combining alkalies with TCE. 2. Glycerine a. Glycerine plus asbestos plus heat causes spontaneous combustion. b. Glycerine plus peroxides provides a combustible material. Wherever possible, glycerine should be replaced with a safer lubricant. All leaks must be eliminated in glycerine handling system to prevent dripping onto hot, insulated surfaces. 3. PDR-1, B-l and B-2 a. A dust explosion is possible with all three solids. b. Spills, when wetted, form an extreme slipping hazard. Normal handling should be designed to avoid excessive dusting in performing the dissolution operation; good housekeeping is necessary in raw material handling areas. 4. Styrene Monomer (Short-Stop Agent) a. Material is a flammable liquid. Bolling Point.......................... l45C (293F) Flash Point ............................. 31C (closed.cup) Explosive Limits ................. 1.1 to 6.1^ by vol. in air b. High vapor concentration irritates eyes and respiratory tract; has an anesthetic acid; threshold limit value is 400 ppm. Material has a disagreeable odor but with good warning properties. Handling of small quantities of styrene in the area should pres nt no great hazards provided material is handled in safety cans, and spills are avoided. RSV0023931 35. 5* Dlallyl Maleate (DAM) a. Eye irritation and dermatitis are the chief hazards of this material. The small quantities in the areas should be moved, sanpled, and handled with care to avoid splashing and spillage; protective equipment of safety glasses and gloves should be employed. 6. Potassium and Ammonium Persulfate a. Moderately toxic material when Inhaled or Ingested; also considered an irritant and allergen. b. Moderate explosion hazard when exposed to heat or chemical reaction causing temperature to rise to 100C. c. Decomposition products Include highly toxic fumes of sulfur oxides. Store in sprinkler protected area and avoid wet conditions around storage area. Spills should be cleaned up Immediately; good housekeeping necessary. 7- Sodium Bisulfite a. Moderately toxic material when inhaled or Ingested. b. When heated to decomposition it emits highly toxic fumes of sulfur oxides. Store in sprinkler protected area and avoid wet conditions around storage area. Spills should be cleaned up immediately; good housekeeping necessary. RSV0023932 36. IX. POLYMERIZATION HAZARDS The following hazards in the polymerization area could cause a leak of flammable materials or produce a source of ignition. All hazards should be eliminated or reduced. A. Accidental Dumping of Reactors It is possible for an operator to open the wrong kettle while preparing to transfer a batch from the kettle to the slurry tank. The high pressure in the downstream equipment will immediately cause VCM to escape into the operating area. It is most probable that the error will be noticed almost immediately and the reactor will be closed again by the operator.* However, should the operator be prevented from so doing by leaks or fumes an explosive situation will result. This problem has been the subject of a PTS project for the past 3 months and it is recommended that the mechanical safe guards under consideration be justified and installed. This will automatically prevent any kettle under pressure from being opened at the dump valve. B. Glycerine Fires It has been shown that asbestos insulation saturated with glycerine will undergo spontaneous combustion at temperatures of approximately 1Q0C. In the past, there has been 3 fires caused in this manner. One involved the insulation on the kettle itself while the two others were with steam pipe insulation. Glycerine has been used ever since the PVC reactors were first installed to serve as a lubricant'and heat removal fluid from the agitator seals. The inability to completely prevent these seals from leaking glycerine onto the kettle surface and the numerous incidents of glycerine leaks in the process lines makes it necessary to replace this material with a less hazardous liquid. Again, this problem has been the subject of an active PTS project for the past three months. The effort has been directed at finding a suitable replacement; G-62 is the current candidate. It is recommended that this project be completed shortly and glycerine be replaced, thus eliminating It from use in the area. RSV0023933 37. C. Deglassed Areas In Reactors Years of manually cleaning the PVC glass lined reactors has resulted In glass damage^ today considerable areas of the reactor have exposed steel. The corrosion of this steel has been noticeable, especially in the copolymer reactors where the acidic batch and the high temp. process water charge have hastened the attack. Although not an urgent problem, this condition cannot be allowed to continue indefinitely. The nickel plating technique has been successfully demonstrated as an economical solution to this problem. It Is recommended therefore that a program and time schedule be defined for the upgrading of all PVC reactors. D. . Lauroyl Peroxide Spillage There is still a noticeable amount of L2O2 spillage occurring during the charging of the 92 Bldg, catalyst bombs. Contact of this material with any hot surface (above 65G} will result in rapid decomposition and the evolution of very flammable gases, with possible autoignition. E. Out-of-Control,, Probable Set-up Batch Listed below are the most probable causes for a batch set-up in each process. Opalon 740 1. Omission of B-l suspending agent 2,, Gross water undercharge 3. Agitator stoppage via power loss 4. Use of antifoam instead of C-l charge 5. Contaminated G-62 Opalon 600 Series 1. Omission of B-l or B-2 suspending agent 20 .Gross water undercharge 3. Agitator stoppage via power loss 4. Use of antifoam instead of C-l charge Opalon 500 series 1. Undercharge or omission of PDR-1 suspending agent 2. Gross water undercharge 3. Agitator stoppage via power loss 4. Aging of PDR-1 solutions at elevated temperatures 5. Iron contamination via RVCM, TCE or water, afferctlng the suspension system. 6. Reflux condenser malfunction RSV0023934 Opalon 400 Series Reflux condenser malfunction 1. The mischarge or omission of B-l and B-2 cannot be detected by quick quantitative tests on the kettle floor, as is the case with the PDR-1 suspending agent. Therefore, it is imperative that the probability of operational error be minimized. It is recommended that the suspension agent charge system be studied and revised to prevent accidental sewering of the charge; it is of greater urgency now with the closed kettle raw material charging technique, since this eliminates the visual check of flow into the kettle. 2. Two water meters in series are used to accurately gauge the process water charge and therefore no "gross water undercharge" can occur. There is a remote possibility that the dump valve might be left open during the raw material charging. Since the kettle water charge is no longer dipsticked for volume with the closed kettle charge technique, reliance is placed on the operator to close the dump valve before proceeding. The use of a "permission switch" should be considered to insure that the dump valve has been closed prior to the start of the raw material charge. It may be possible to combine this device with the work aimed at automatically preventing the dump of a pressurized kettle. 3. Further improvements to prevent uncontrolled agitator stoppage is not warranted since power failures are so few and satisfactory emergency procedures exist. 4. The use of the wrong liquid material for C-l suspending agent charge can lead to gross problems. The proba bility of human error has been Increased by the large number of drums now necessary for kettle operation; antifoams, G-62, glycerine and C-l are all handled the same way with unit charges being transferred from a 55-gallon drum to a container.' Compounding the problem area is the limited space for drum shortage with the consequence that no definite location exist for each drum of raw material. The overall problems of housekeeping, warehouse storage. Inventory control, identification of materials, and transporting material should be reviewed and Improvements (capital expenditure) requested to upgrade this operation. RSV0023935 39- 5- At present G-62 Is filled in 85 Bldg, into reclaimed 55 gallon drums. If a cleaned, reclaimed drum is not used then possible contamination is introduced into the operation. A better method for control and transporting this raw material is necessary now with the high usage rates in PVC operation. 6. Reflux condenser malfunction does occur but warning signals provide ample time to correct the problem. RSV0023936 40. II. EMERGENCY PROCEDURE The emergency procedures now in use are concise, precise and up to date. They are posted on each kettle floor and easily available to the operating personnel. These procedures cover the action to be taken for (a) Evacuation (b) Fire (c) Power or Agitator Failure (d) Water Failure ej Air Failure and (f) Major YCM Spills.. In addition, corrective action for any process abnormally is defined in the SDP, with an up to date copy on each kettle floor. During this audit, the general emergency procedures were reviewed with the objective of developing even faster, simpler and better procedures via nominal equipment installations. It is recommended that the following changes be made. A. Styrene Injection System The present injection systems require a man to carry a one gallon safety can filled with styrene to a kettle, manipulate valves, add styrene to a bomb and then open a kettle valve to drain the styrene into the batch. This system is perfectly adequate when only one kettle is Involved in the emergency. For multiple kettle emergency, which exist during any of the above listed problems, the styrene addition procedure requires too much time. Hence, for example the evacuation procedure does not call for styrene injection. In addition to the time factor, the addition.of styrene to a non-agitating (power failure) venting batch via the overhead injection system will not be completely effective. Much of styrene will be volatlzed and lost before sufficient mixing is achieved. The system defined below will eliminate both these deficiencies by instantaneously Injecting styrene into all kettles in a building via the sub-liquid step bearing water flush system. 1. Install a 10 gallon pressure vessel to contain styrenej locate immediately behind the control panel at the step bearing rotameter station. 2. Connect the 10 gallon container to the main high pressure water line feeding the manifold; install block valves on the water line and the styrene line. 3. Install a high pressure vessel to serve as a nitrogen reservoir; the nitrogen pressure will be used to force the styrene through the step bearing system against the kettle back pressure. RSV0023937 41. 4. Three fast acting valves with extension handling at the front side of the control panel, would permit rapid (less than 10 seconds) pressurization of the styrene container, water shut-off to the step bearing and styrene addition to the kettles. B. Full Cold Water to Reactor Jackets By installing a readily available block valve on the instrument air supply all instruments can be made to "fall safe" thus supplying full cold water to each kettle jacket. C. Air Failure By installing a pressure reducer and connecting the available new plant nitrogen supply line in the building to the instrument air supply, a simpler and easier to operate emergency system can be effected. The problems associated with serving nitrogen cylinder and switch over would be eliminated. D. Emergency Panel It would be desirable to install the above features together with the presently installed safety devices so that all operations are centralized at one point -- at an emergency control panel. E. Revised Emergency Procedures The following revised Emergency Procedures should be Introduced with the modifications to the (a) styrene Injection system, (b) full cold water system, and (c) air failure system. ,, ._ 1. Evacuation Procedure Series of Short Blasts .......... Evacuate after carrying out emergency procedure One Long Blast ............................. Evacuate immediately Procedure after Short Blasts a. Stop VCM and VAc pumps. b. Close valves before VAc and VAc meters c. Put kettles on full cold water by closing air supply valve. d. Inject styrene into all kettles. e. Proceed immediately to assembly area. Primary Assembly Area............... Area south of 89 Bldg. (warehouse) Secondary Assembly Area .... Area east of 8l Bldg. RSV0023938 42. 2. Fire (a) Attempt to control and extinguish fire with extinguishers in the area. Do not use water on electrical equipment fires. (b) Immediately instruct nearest by-stander to turn in the alarm. Use Fire Phone - NE corner 88 Bldg. - NE corner 85 Bldg. Telephone 2771 (c) Immediately sound Evacuation Alarm Short Blast .......... If fire cannot be rapidly extinguished and aid in fire fighting is required. Long Blast ............ Uncertain about the fire controllable or if the fire is in the polymerization area. 3. Power Failure or Agitator Failure Prompt, positive action must be taken Immediately; do not wait to determine if power will be restored shortly. (a) Stop all VCM and VAc addition to kettles and . close valves. (b) Put all kettles on full cold water by closing . air supply valve. (c) Inject styrene into all kettles, use maximum settings for all rotameters supplying full kettles. (d) Vent each operating kettle to the stack for minute in rotating to supply cooling and agitation. () Monitor kettle pressures; vent high pressure kettles continuously using stack by-pass valve. (f) When power is restored; (1) Start all jacket water pumps. (2) Jog kettle agitator for a second; keep repeating until pressure kick subsides, then leave agitator on. (g) If at any time a kettle pressure is completely out-of-control sound the Evacuation Alarm and proceed to the assembly area. RSV0023939 43. 4. Water Failure Prompt positive action defined below must be taken immediately; do not wait to determine if water will be restored shortly. a. Immediately stop all VCM and VAc additions to kettles and close valves. b. Close Instrument air supply valve. c. Inject styrene to all kettles; use maximum settings for all rotameters supplying full kettles. d. Vent each operating kettle to the stack for one minute in rotation to cool kettle contents. Simultaneous to the above action, the Foreman and assistants will switch over to auxilllary water supply. a. Close main supply SW corner of 88, 1st floor SE corner of 92 Warehouse (behind Vredomatlc) b. Open auxllliary supply SW corner of 88, 1st Floor NW corner of 92 Warehouse (behind screen) 5- Mr Failure a. Close main air supply valve at control panel. b. Open nitrogen air supply valve at control panel. RSV0023940 Safety in t&e Scale-ufe and @wUcal 'PnaceddeA PURPOSE Many accidents have occurred in the chemical manu facturing industry for lack of complete process informa tion in the operating ranges of plant or pilot plant equipment. Sometimes this has occurred because of inadequate small-scale studies to specify safe operating procedures and appropriate equipment for the larger scale work. Sometimes there simply has not been established a mechanism for checking all the critical areas providing background knowledge necessary for safe operation. This Safety Guide has been developed to assist chemical manu facturers in the preparation of such a mechanism. SCOPE This Safety Guide covers the following situations: 1. Scale-up within a given laboratory or pilot plant establishment. 2, Scale-up and transfer of a process from pilot plant to a manufacturing plant for commercial or semicommercial production. RESPONSIBILITY The primary responsibility for obtaining necessary process information, including that on safety aspects, lies with laboratory and pilot plant group leaders and their technical people. This responsibility is an integral part of their jobs and cannot be delegated elsewhere. The responsibility begins as soon as work is started on the process, whether on laboratory, pre-pilot, or pilot plant scale. The areas of consideration normally covered are outlined in the check list provided with this Safety Guide. It has been found that a guide of this type is desirable in all stages of process development. It becomes most urgent from the safety aspect when scale-up from one stage to another is planned. It should be borne in mind that certain of the items on the check list may not be critical in small scale operation but highly critical upon scale-up. When transfer of a product from pilot plant to a production unit is contemplated, review of process data, using the check list as a guide, should be started with the plant people as early as possible before transfer. The plant safety engineer should be included in discus sions and should receive full information on process safety. The Manufacturing Department has the responsi bility for the safety of its personnel and the protection of its equipment. It must have complete information on which to base a judgment of the hazards of manufac turing any new product. SAFETY CHECK LIST FOR PROCESS General Considerations Review with Safety and Fire Protection engineers and the Manufacturing Department a complete end-to-end narrative of the process with a flow-sheet of the pro posed equipment. Set up a complete material balance on the equipment flow-diagram. Define potential pollution and hygiene problems as well as physical and chemical hazards. Examine the process and the flow-sheet specifically for the consequences of operator errors and malfunction of equipment. Process procedure and equipment should be thoroughly examined and attempts made to visualize effect of variations in temperature, pressure, sequence of addition of materials, and/or proportion that may result through misoperation or mechanical failure. Before operating instructions are finalized for the process of any part thereof, it is suggested that a job safety analysis be performed. This is a study of the operation, element by element, to identify and to antici pate hazards and to remove them or to neutralize them by specific means. Detailed Information Safety factors cannot be isolated. Process safety across a scale-up is an integral part of many inter-related factors including types of equipment, process variables, proper ties of materials in process, manning, etc. Based on this premise, the following check-list has been designed to provide the background knowledge for anticipating and minimizing hazards. Product Name Composition Structure (s) Molecular Weight (s) Physical Properties Uses Production Volumes and Estimated Costs Tentative Specifications Storage and Handling Requirements RSV0023942 Chemistry of Process Reaction Equations Reaction Conditions, e.g. time, temperature, pressure, solvent, catalyst, order of addition of materials, etc. Safe Parameters of such important variables as tempera ture, pressure and pH. Process kinetics and thermochemistry Known side reactions Possible side reactions Product stability to heat, light, air, water, storage Stability of reactants Raw Materials Names, structures, compositions Physical properties Sources Tentative specifications Stability data Storage and Handling Requirements Process Flow Sheets Materials flow streams Heat duties, and other services Labor requirements r Select equipment and protection that will provide safe operation. Equipment and Instrumentation Description Design data Materials of construction Effect of improper control or side reactions on materials Manufacturers or suppliers Safety Considerations Chemical hazards; Heat effects and rate effects in main reaction and side reactions. Stability of reactants and products to heat, light, air, water, pH changes, pressure, etc. Effects of excess or deficiency of one or more reactants. Possible induction effects, hang-fire reactions. Estimated decomposition energies of reactants and products. Flammability characteristics of materials, e.g, flash point, explosive range, auto-ignition temperatures and other pertinent characteristics. Hazards of drying and grinding. Equipment hazards: Effect of power failure, vacuum failure, air leakage, etc. Fouling of heat transfer surfaces and instrument sensing units. RSV0023943 Health hazards: Acute and chronic toxicity data on reactants, products and by-products should include oral, dermal, vapor and eye data. First aid treatments and antidotes for various exposures. Notification of medical department of work on toxic materials. Procedures for safe handling of materials. Procedures for decontamination of toxic or obnoxious materials. Operating Procedures Detailed description of recommendations. Possible effects of deviations from recommended range of operating variables on safety of operation. Preparation of step-operating chart. Procedure for discarding unsatisfactory product or intermediates. Procedure for waste disposal. Emergency shut-down procedures, or what to do in the event of having to kill a reaction. Analysis and Process Controls Analysis of reactants and products Controls during processing: Physical methods, Chemical methods Final Product Labeling Requirements Container Type and Size Pertinent ICC Regulations Shelf-life or storage stability Any special warehousing requirements Sensitivity to contamination t ....... .. . .... .*7. fc.'A.. -------- .-------.-- --- ------d Make certain that personal protective equipment is specified where required. FEEDBACK A process transfer is not complete until a satisfactory operating process or plant is turned over to a manufactur ing unit. In the period between the transfer to those doing the scale-up and final transfer to manufacturing, many inadequacies in the original experimental data often show up. It is well to document, with explanation, all of the principal precautions which have been found necessary for the safe operation of the process. Feed back of this information to research and development should result in a continuing improvement of process transfers. The information and recommendations contained in this publication have been compiled from sources believed to be reliable and to represent the best current opinion on the subject. No warranty, guarantee or representation is made by the Association as to the absolute correctness or sufficiency of any representation contained in this and other Safety Guides and Manuals, and the Manu* facturing Chemists' Association assumes no responsibility in connection therewith; nor can it be assumed that all acceptable safety measures are contained in this and other Safety Guides and Manuals, or that other or additional measures may not be required under particular or exceptional conditions or circumstances. Price: 20 cents per copy. For copies of this pamphlet and a list of other available safety publications write: Manufacturing Chemists' Association, Inc., 1825 Connecticut Avenue, N.W., Washington 9, D. C. RSV0023944 Health hazards Acute and chronic toxicity data on reactants, products and by-products should include oral, dermal, vapor and eye data. First aid treatments and antidotes for various exposures. Notification of medical department of work on toxic materials. Procedures for safe handling of materials. Procedures for decontamination of toxic or obnoxious materials. Operating Procedures Detailed description of recommendations. Possible effects of deviations from recommended range of operating variables on safety of operation. Preparation of step-operating chart. Procedure for discarding unsatisfactory product or intermediates. Procedure for waste disposal. Emergency shut-down procedures, or what to do in the event of having to kill a reaction. Analysis and Process Controls Analysis of reactants and products Controls during processing: Physical methods. Chemical methods Final Product Labeling Requirements Container Type and Size Pertinent ICC Regulations Shelf-life or storage stability Any special warehousing requirements Sensitivity to contamination Make certain that personal protective equipment is specified where required. FEEDBACK A process transfer is not complete until a satisfactory operating process or plant is turned over to a manufactur ing unit. In the period between the transfer to those doing the scale-up and final transfer to manufacturing, many inadequacies in the original experimental data often show up. It is well to document, with explanation, all of the principal precautions which have been found necessary for the safe operation of the process. Feed back of this information to research and development should result in a continuing improvement of process transfers. The information and recommendations contained in this publication have been compiled from sources believed to be reliable and to represent the best current opinion on the subject. No warranty, guarantee or representation is made by the Association as to the absolute correctness or sufficiency of any representation contained in this and other Safety Guides and Manuals, and the Manu facturing Chemists' Association assumes no responsibility in connection therewith; nor can it be assumed that all acceptable safety measures are contained in this and other Safety Guides and Manuals, or that other or additional measures may not be required under particular or exceptional conditions or circumstances. Price: 20 cents per copy. For copies of this pamphlet and a list of other available safety publications write: Manufacturing Chemists' Association, Inc., 1825 Connecticut Avenue, N.W., Washington 9, D. C. RSV0023945 PRESENTLY USED RAW MATERIALS Material_________ Container ____________ Form frank Drum Bag or Prime Hazard frlber Drum _ 1. VCM L,V 2. VAC L 3- THF L 4. DEM L 5- A-6 6. L202 S,L S. 7- DAM 8. NH40H L L 9- NaOH 10. Ca(OH)2 SjL SjL 11. TCE _ L_ 12. Glycerine L 13. PDR-1 S,L 14. B-l S^L 15- B-2 S,L 16. Sterox 110 L. 17- Lauryl Alcohol L 18. Nopco NXZ L 19- Hallco 20. C-l L L e D-l S * G-62 L 23- Styrene 24. Duponal ME L S,L 25. Duponal WAQM L_ 26. Sodium Bisulfite SjL 27. Sod.Bicarbonate SjL 28. GMS S_ 29. Pot.Persulfate 30. Amm.Persulfate S,L S,L 31. Laurie Acid S 32. Normal Octanol L X X X X Special X X X XX XX XX XX X X X X X X X X X X X X X X X X X X X X X X X X X X X Fire & Explosion Fire & Explosion Fire & Explosion Irritation Fire & Explosion Fire & Explosion Irritation Eyeburn Eyeburn Eyeburn Irritation Fire Slipping Slipping Slipping Slipping Eye Irritation Slipping Slipping Slipping ___ Slipping Fire & Explosion Eye Irritation Eye Irritation Eye Burns __-- ___ Irritant Irritant Eye Irritation Irritant Protective Equ: !T 2 3 4 5 6 ' XX Xx ; Xx : XX XX X XX Xx ; XXX XX XXX X XX X X X X X X X X X XX X X XX X X XX XX X XX CODE: S -- Solid L -- Liquid 1 = Safety Glasses 2 -- Safety Goggles 3 = Face Shield 4 = Rubber Gloves 5 = Rubber Apron 6 Respirator 7 = Scott Air-Pack (heavy cone.) RSV0023946 SUSPENSION AREA RAW MATERIALS - MIXING VIA SPILLS 4aH> <UU oOJ oE<oSfcuWiElWEH i hi '-iOceOug h.i hiqiIrKO-1ifOhHOnJOK-fpan) r--op>|>ooooo* nEjao-p); A-3 iH OJ LfN^O N-00 ON rHiHrHr-- 1. VCM X 111111111 11111111111 2. VAC Xllllllll 11111111111 3. THF Xlllllll 11111111111 4. TCE X33333443333333343 5. DAM X 33 334 433333333 33 6, DEM X333443333333333 7. Glycerine X22442222222222 8. G-62 X 2 4 4 22222222 22 9. C-l X4 422222222 22 10. A-6 X 4444444444 4 11. L202 X4444444444 12. D-l X22222222 2 13. B-l X2222222 2 14. B-2 X2 2222 2 2 15* PDR-1 X 2222 3 2 16. Hallco X22 2 2 2 17- Sterox 18. Dytoi X 22 22 X 22 2 19. Nop co X22 20. Lime x4 21. Water X CODE: 1 *= Physical facilities and raw material characteristics such that mixing only possible in kettle. 2 = No hazard (except possible slipping hazard. 3 = A potential hazard exists, either separately or together 4 = A known serious hazard. COMMENTS: (a) Spillage of A-6 and L02 constitutes a serious hazard at all times. (b) TCE + Lime --^ Dichloroacetylene (explosive) (c) Spillage of TCE, DEM or DAM constitutes a potential hazard. (d) Lime with water or aqueous material can generate heat resulting in splattering. RSV0023947 a-4 l. 2. 3. 4. 5- 6. 7- 8- . 9- 10. 11. 12. 13- EMULSION AREA RAW MATERIALS - MIXING VIA SPILLS NAOH,Flake m TB CTv pH CV1 a oa 83 aa i--1 oi oCO C\J ocO OJ on ft o ` CO CO cu 3 s aaa v--' ' o on -3- in MO X43 33 3 rH O c as pH pH on os s; OS po o 1 a oo 5 a G C? p O< aa 6 3 o r- CO <j\ o rH 33 3 3 o OJ u qo p Ot OS CO a pH CVJ pH H 34 o 1 T3 H 3 O < oi-1n 3 NH40H,29# X3 33 3333 3 33 3 K2S208 X 23 2222 2 22 2 (NHi|)2S208 X2 2222 2 22 2 NaHS03 X 2223 2 22 2 GMS X222 2 22 2 N-Octanol X2 2 2 2 2 2 NaHC03 X2 2 22 2 Duponal WAQM X2 22 2 Duponal ME X 22 2 Span 20 X2 2 Water X2 Laurie Acid X CODE; 1. Mixing only possible in kettle. .2 No hazard (except possibly slipping hazard. 3- Potential hazard exists, either separately or together. 4. A known serious hazard. COMMENTS: (a) Caustic spillage will be serious if in contact with limited amount of water. (b) Ammonium Hydroxide spills always a potential hazard. (c) The persulfate and bisulfite can be serious if temperature Increases and causes decomposition. RSV0023948