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A BATCH POLYSTYRENE REACTOR RUNAWAY: A CASE HISTORY BY RONALD J. WILLEY, PhD. PE. NORTHEASTERN UNIVERSITY PREPARED FOR

A BATCH POLYSTYRENE REACTOR RUNAWAY: A CASE HISTORY BY RONALD J. WILLEY, PhD. PE. NORTHEASTERN UNIVERSITY PREPARED FOR SACHE A PRODUCT OF THE CCPS-AICHE NEW YORK, NEW YORK  2000. ST. LAWRENCE RIVER. PROVINCE OF QUEBEC CANADA. ISLE OF MONTREAL. LACHINE CANAL. LASALLE. THE ACCIDENT

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A BATCH POLYSTYRENE REACTOR RUNAWAY: A CASE HISTORY BY RONALD J. WILLEY, PhD. PE. NORTHEASTERN UNIVERSITY PREPARED FOR

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  1. A BATCH POLYSTYRENE REACTOR RUNAWAY: A CASE HISTORY BY RONALD J. WILLEY, PhD. PE. NORTHEASTERN UNIVERSITY PREPARED FOR SACHE A PRODUCT OF THE CCPS-AICHE NEW YORK, NEW YORK 2000

  2. ST. LAWRENCE RIVER PROVINCE OF QUEBEC CANADA ISLE OF MONTREAL LACHINE CANAL LASALLE

  3. THE ACCIDENT OCTOBER 13, 1966 LATE EVENING INITIAL EVENT STYRENE VAPOR COMBUSTION

  4. BACKGROUND

  5. 5POLYMERIZATION REACTORS IN THE BUILDING2 REACTORS WERE USED FOR THE PROCESS DESCRIBED BELOW

  6. PHYSICAL PROPERTIES OF STYRENE·MOLECULAR WEIGHT 104.5·BOILING POINT 145C·FREEZING POINT -30.6C·FLASH POINT 31C·AUTOIGNITION TEMPERATURE 490C CH=CH 2

  7. ADDITIONAL PROPERTIES OF STYRENEFLAMMABLE LIMITS IN AIR (VOL%) 1.1 TO 6.1OSHA PEL 50 PPMWILL POLYMERIZE AT ROOM TEMPERATURE IF UNINHIBITEDHEAT OF POLYMERIZATION 74.5 MJ/KMOLCP, HEAT CAPACITY 1.69 J/G

  8. ARRHENIUS EQUATIONk Rate constantA Pre-exponential constantEa Activation energyR Gas ConstantT Absolute temperature

  9. EQUATIONS TO PREDICT TIME, Dt, TO RUNAWAYa is a proportionality constantT1 is the initial temperature

  10. ADIABATIC TEMPERATURE RISE OF CATALYZED STYRENE (HYPOTHETICAL EXAMPLE) from Boyle 100 o C, 10 MIN TO RUNAWAY At ~130 t, MINUTES 10 D 1 TIME, 0.1 100 150 200 o BATCH TEMPERATURE, C

  11. STYRENE POLYMERIZATION METHODSANIONIC POLYMERIZATIONCATIONIC POLYMERIZATIONFREE RADICAL POLYMERIZATIONZIEGLER NATTA POLYMERIZATION

  12. FREE RADICAL POLYMERIZATION INITIATION . . CH=CH CH-CH R CH-CH R 2 + R . 2 2 . PROPAGATION R . n + D

  13. STYRENE TO POLYSTYRENE BATCH PROCESS1. LOAD THE REACTOR WITH STYRENE2. ADD POLYMERIZATION CATALYST3. HEAT TO 95°C4. HOLD FOR 2 TO 8 HOURS

  14. STYRENE TO POLYSTYRENE BATCH PROCESS CONTINUED5. TRANSFER TO FORMING UNIT AT ABOUT 75% CONVERSION6. OPEN FORMING UNIT AFTER FULL CONVERSION. REMOVE PS BLOCK7. CRUSH PS BLOCK8. TRANSFER SOLIDS TO EXTRUDER

  15. THE RELIEF SYSTEM TO ROOF OUTSIDE BUILDING SIGHT GLASS RUPTURE DISC REACTOR INSIDE BUILDING

  16. TIME LINE EARLY IN THE DAY OF EXPLOSIONTIME NOTE2:30 POLYMER A PRODUCED19:30 STARTED POLYMER B BATCH19:30 LOADED MATERIAL19:40 STARTED HEATING21:15 HEATED TO 92°C

  17. TIME LINE BEFORE EXPLOSIONTIME TEMP,C NOTE21:15 92 21:45 110 R.O. (REACTOR OPER.) IN CANTEEN21:51 115 21:55 119 22:00 126 R.O. RETURNED FROM CANTEEN

  18. TIME LINE MINUTES BEFORE EXPLOSIONTIME TEMP,C NOTE22:02 130 R.O. CHECKS IN22:03 132 R.O. ORDERS DUMP22:04 137 3 MEN ATTEMPT DUMP22:07 170 R.O. ORDERS 3 BOLTS ON FLANGE22:08 R.O. ORDERS EVACUATION

  19. ??HOW DID STYRENE FOG ENTER THE INTERNAL BUILDING??

  20. INVESTIGATIONCOMPARISON/CONTRAST OF TWO REACTORS ITEM REACTOR 1 REACTOR 2 (THE OTHER) (THE SUSPECT) RUPTURE DISC INTACT RUPTURED MANWAY INTACT INTACTDUMP VALVE CLOSED 1/4 OPENSIGHT GLASS INTACT MISSINGANSWER: FAILED SIGHT GLASS

  21. Courtesy Prof. Chuck Sheppard, Univ. of Tulsa

  22. A CONFINED SPACE EXPLOSION

  23. EXTENT OF EXPLOSION11 PEOPLE KILLED130 TON CAR OF VINYL CHLORIDE TIPPED OVERGUARDHOUSE DESTROYEDBRICKS FOUND 400 FEET AWAY

  24. TNT EQUIVALENTBASED ON THE ESTIMATED OVERPRESSURES AND AMOUNT OF STYRENE RELEASED BEFORE THE INITIAL COMBUSTIONTHE COMBUSTION WAS AS IF 6.6 TONS OF TNTEXPLODED AT ONCE

  25. FIRE PROTECTION SYSTEMSSPRINKLER SYSTEMSFIRE WATER PUMPSFIRE RATED WALLS AND BARRIERS

  26. BROKEN SPRINKLER MAIN REMAINS OF POLYMERIZATION BUILDING

  27. PROPERTY DAMAGE SUMMARYPOLYSTYRENE BUILDING DESTROYEDBUILDINGS 1,4,5,8,&12 SUFFERED FIRE AND WATER DAMAGEPUMP HOUSE DESTROYEDSEVERAL AUTOMOBILES DAMAGED

  28. INVESTIGATIONSEARCH FOR THE ROOT CAUSEPRINCIPAL CAUSE – RUNAWAY REACTION CAUSED A PRESSURE BUILDUP INSIDE A REACTOR THAT SUBSEQUENTLY RELIEVED.ALL MATERIAL RELIEVED SHOULD HAVE EXITED BUILDING THROUGH ROOF VENT.

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