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Assessing storage of unstable materials before next processing step (Adapted from Worked Example 2.

1 in "Ch2: Fundamentals of Thermal Process Safety, Thermal Safety of Chemical Processes: Risk Assessment and Process Design, Francis Stoessel, 2008 Wiley-VCH) Problem Statement Product at 90 C stored in an unstirred jacketed vessel heated with hot water Product degrades at a rate of 1%/day if held at 90 C DSC thermogram in closed pressure resistant crucible at scanning rate of 4 K/min of the product shows exothermal peak starting at 200 C, with energy of 800 kJ/kg Product is close to its melting point Mass of product to be stored is 2600 kg Determine Assess if storage over the weekend will cause any problems or safety issues. Determine if the decomposition onset temperature of 200 C will be reached over the weekend. Assumptions Without stirring, heat transfer on the scale mentioned is POOR, adiabatic conditions would be a worst case estimate Van't Hoff's rule of reaction rates doubling every 10 K increase Constant specific heat of the product melt is ~ 2 kJ/kg/K Calculations cp = Q= rate = To = q= t (h) 0 40 60 70 75 77.5 2 800 1 90 92.59 T (C) 90 100 110 120 130 140 kJ/kg/K kJ/kg %/day C mW/kg specific heat of product melt heat of reaction / decomposition rate of product decomposition initial storage temperature initial specific heat release rate

Tdot (K/hr) Tdot_avg (K/hr) 0.17 0.25 0.33 0.5 0.67 1 1.33 2 2.67 4 5.33 8

78.75 79.375 79.6875 79.84375 79.92188 79.96094 Conclusion Total time =

150 160 170 180 190 200

10.67 16 21.33 32 42.67 64 85.33 128 170.67 256 341.33

80.0

hr

In this approximate calculation, it is very likely that the onset temperature of the decomposition of the product melt will be reached.

cp = r= - D HR = T0 = E= k0 = R=

2 850 150 298 50000 0.01 8.314

kJ/kg/K kg/m3 kJ/mol K J/mol mol/m3/s J/mol/K

specific heat of reaction mixture density of reaction mixture heat of reaction cooling medium temperature activation energy of reaction pre-exponential factor for zero order reaction ideal gas constant

Critical Cooling Medium Temp Calc dTcrit (guess) = dTcrit (calc) =


2

16.4

critical cooling medium temperature difference, guess critical cooling medium temperature difference, calc

16.4 K Err = 5.05E-29 K2 Tcrit = 314.4 K

critical cooling medium temp

Time of No Return Calc q0' = TNR = 1.76 10577 2.9 W/kg s h specific initial heat release rate time of no return (time elapsed after which even with full cooling switched on, reactor cannot be cooled)