Accelerating rate calorimeter and its application in the thermal hazard evaluation of chemical production

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1 Journal of Safety Science and Technology Vol. 1 No. 4 Aug X(2005) ,, (, ),, ; ; X A Accelerating rate calorimeter and its application in the thermal hazard evaluation of chemical production QIAN Xin2ming, LIU Li, ZHANGJie (State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing ) Abstract This paper introduced an new instrument which was used in thermal hazard analysis accelerating rate calorimeter (ARC). Its design principle and inner structure, run modes and the data types including temperature,pres2 sure and the time to maximum temperature rise rate were presented. The application of ARC in thermal kinetic study, self2accelerating decomposition temperature calculation, chemical technical safety and process development and accidents investigation were introduced. the characteristics and predominance of ARC were drawn in thermal hazard evaluation of chemical production Key words accelerating rate calorimeter ;thermal hazard ;chemical production 1 Accelerating Rate Calorimeter (ARC) 1970, DOW, Columbia [1-3 ] Scientific, Acceler2, ating Rate Calorimeter(ARC g ) ,,,,,, 3 ( ),

2 14 1 (ARC), 2 ( ARC) ARC,, [4-6 ] 211 ARC 1 ARC,,, - -, ( 0102 / min),, 1 ARC 2 ARC H2W2S, ARC [7 ] 3 ARC 3,,, ARC 4,3 N ( ) , -, ARC 311, 3,, ARC T ARC - - ( 0, T f, H2 W2S) ( T ISO) ad 18115, H2W2S ( 2),

3 4 15 (a) 2 ; (b) 2 3 ARC 312 (a) - ; (b) - ; (c) - ; (d) (a) (c) Gassy ARC 440K ( 4 (b) ) 4,

4 16 1,,, 313 (TMR), Yin Fangdong TMR,,, [9 ], ( (1) ( t mr ) T = RT 2 mr Ae - E/ RT C n E (1), E,, 1 [8 ] - ARC T 02 (1) Townsend Tou [6 ] ARC, ARC 1 T ad,1 = 2 T ad,2 (3) 1 T 01 = R Ea ln 1 2 ( dt/ dt) 01 ( dt/ dt) 02 (4),, ( dt/ dt) 1 = 2 Ea 1 1 exp - - (5) ( dt/ dt) 2 1 R T 1 T 2 ( 5) Horng2Jang Liaw [10 ],, 4 ARC 4. 1, HA2 ZOP,FMEA, ARC - 5 ARC 314 (6), H r = MC v T ad (6) ARC n, ( ) dt [6 ] = Ae - E n T f - T RT T dt T ad C n - 1 A (7) ad 0 = 1 + m b / C b / m s C s (2) E, m s, m b ; A [11 ] C 1/, ( 1 ) ( 2, 2 = 1)

5 4 17 Kohlbrand [12 ] SimuSolv T SADT ARC T SADT,, T SADT Townsend Kohlbrand [13 ], T SADT Frank - Kamenetskii Melhem,Fisher Shaw [14 ] [18 Thomas ] 4. 3 Ahmed [15 ] KP ( kinetic pa2, ; rameterization) ; ;, ARC [19, ],, 160 ARC 150, [16 ( T SADT ) ] T SADT, 7, 6 Semenov (0105 Torr) 140 Arrhenius,, 4. 4, T SADT, ARC, T NR T NR Snee, DSC ARC DSC 240, ARC, 6 Semenov 42, T SADT T NR [ ] ARC Cardillo ARC, , [22, 100Kg ] Steve ARC, [23 ] /, R ( T NR ) 2 40 T SADT = T NR - (8) E, ARC DIERS(De2 Wilberforce [17 ] sign Institute for Emergency Relief Systems),,ARC, - T NR, [24,25 ]

6 18 1 [11 ]. [ ]. 5,2003 [12 ] Kohlbrand, H. T., The use of SimuSolv in the Modeling of ARC Data, Proceedings of the international symposium on runaway reactions, , CCPS (AIChE) / I. Chem. E., Cambridge, MA, 1989, [13 ] D. I. Townsend, H. T. Kohlbrand, Cont. Rev. Chemical Runaway Reactions, IBC Amsterdam 86 [ 14 ] Melhem, G. A.,Fisher, H. G., and Shaw, D. A., An Ad2 vanced Method for the Estimation of Reaction Kinetics Scale2, up, and Pressure Relief Design, Process Safety Progress,, 1995, 14(1), 1-21 [ 15 ] Ahmed, M., Goetz, D. D., Fisher, H. G., and ASTM 1998 Janeshek, A. M. Reaction Model from Adiabatic Calorimeter Data In Proceeding of the Tnternational Symposium on run2 ARC ARC away Reaction and pressure relief design, 1995, [16 ] United Nations. Recommendation on the transport of danger2, ous goods, manual of tests and criteria 3rd revised edn., [26 ] 1999 [17 ] Wilberforce J. K.. The Use of Accelerating Rate Calorimeter to Determine the SADT of Organic Peroxides. Columbia Sci2 entific Industries, Milton Keynes, 1981 [1 ] A. Benuzzi, J. M. Zaldivar, Safety of Chemical Batch Reac2 torsand Storage Tanks, Kluwer Academic Publishers, Boston, 1991 [2 ] T. Grewer, Thermal Hazards of Chemical Reactions, Elsevi2 er, New York, 1994 [3 ] D. Frurip, A. Chakrabarti, et al., in Proceedings of the International Symposium on Runaway Reactions and Pressure Relief Design, American Institute of Chemical Engineers, New York, 1995 [4 ] Townsend, D. I. ; Tou, J. C. Thermochim. Acta,1980,37 1 [5 ] Coates,C. F. Chemistry and Industry,1984,3 [6 ],,,.,2001,10 (3) 149 [7 ] Towsend D., Fergnson H., and Kohlbrand H. Application of ARC Thermokinetic Data to the Design of Safety Schemes for Industrial Reactors. Process Safety Progress, 1995, 14 (1), [8 ] Wilberforce J. K. Comparison of Methods of Determination of Adiabatic Times to Maximum Rate of Exothermic Reactions. Journal of Thermal Analysis, 1982, [9 ] Yin Fangdong. Adiabatic calorimeter Adiabatic calorimeter Fundamentals and application in thermal hazard evaluation. In Proceeding of the International Symposium on runaway Reaction and pressure relief design, 1995, [10 ] Horng2Jang Liaw Ching2Chir Yur Yung2Fen Lin. A mathe2 matical model for predicting thermal hazard data. Journal of loss prevention in the process industries. 2000, 13(6) [18 ] Mores S. Nolan P. F. O Brien G. Determination of the Self Accelerating Decomposition Temperature ( SADT) from Thermal Stability Data Generated Using Accelerating Rate Calorimetry. I ChemE Symposium, Manchester,April, 1994 [19 ] Coates C. F. The A. R. C. in Chemical Hazard Evaluation. Chemistry & Industry March 1984, 212 [20 ] Kohlbrand H. T. Reactive Chemical Screening for Pilot Plant Safety. Chemical Engineering Progress April 1985 [21 ] T. J. Snee. Incident Investigation and Hazard Evaluation Using Differential Scanning Calorimetry and Accelerating Rate Calorimetry. J. Occupational Accidents 1987, 8, [22 ] Cardillo P. Thermal Decomposition of 32Amino252methyl Isoxazole. J. Loss Prevention 1988, 1(1) [23 ] Steve S. Y. Wang, San Kiang, William Merkl. Investigation of a Thermal Runaway Hazard - Drum Storage of Thionyl Chloride/ Ethyl Acetate Mixture. Prepared for presentation at 1994 AlChE Spring National Meeting 28th Annual Loss Pre2 vention Symposium [24 ] De Haven E. S. Approximate Hazard Ratings and Venting Requirements from CSI 2 A. R. C. Data. Plant/ Operations Progress 1983, 2, 21 [25 ] Emergency Relief System Design Using DIERS Technology2 The Design Institute for Emergency Relief System(DIERS) Project Manual. American Institute of Chemical Engineers, New York [26 ] ASTM. Standard Guide for Assessing the Thermal Stability of Materials by Methods of Accelerating Rate Calorimetry. E , 1998

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