Thermal hazardous evaluation of autocatalytic reaction of cumene hydroperoxide alone and mixed with products under isothermal and non-isothermal conditions

• Published in: Journal of thermal analysis and calorimetry Vol. 140; no. 5; pp. 2325 - 2336
• Main Authors: Liu, Shang-Hao, Yu, Chang-Fei, Das, Mitali
• Format: Journal Article
• Language: English
• Published: Cham Springer International Publishing 01.06.2020; Springer; Springer Nature B.V
• Subjects: Acetone; Activation energy; Adiabatic conditions; Analytical Chemistry; Chemical process industries; Chemistry; Chemistry and Materials Science; Cogeneration; Cogeneration power plants; Cumene; Cumene hydroperoxide; Curve fitting; Decomposition; Decomposition (Chemistry); Decomposition reactions; Dicumyl peroxide; Enthalpy; Exothermic reactions; Explosions; Heat transmission; Heating rate; Inorganic Chemistry; Measurement Science and Instrumentation; Numerical analysis; Operational hazards; Organic peroxides; Parameters; Peroxides; Physical Chemistry; Polymer Sciences; Polymerization; Reaction kinetics; Temperature profiles; Thermal decomposition; Thermal instability; Autocatalytic reaction; ARC; CHP; DSC; Runaway reaction; Activation Energy
• ISSN: 1388-6150; 1588-2926
• DOI: 10.1007/s10973-019-09017-7

Severe fire and explosions are frequent phenomena during handling of organic peroxides that are promoted supremely by conditions such as chemical impurities and thermal instability. As an initiator in the polymerization process, cumene hydroperoxide (CHP) has wide usage in the chemical process industry. This violently reactive chemical is studied here experimentally using differential scanning calorimeter (DSC), an isothermal mode of operation that can access the thermal hazards in the decomposition of CHP alone and later mixed with products following an autocatalytic reaction scheme. Importantly, DSC-evaluated thermokinetic parameters such as reaction enthalpy (Δ H d ), time to maximum rate (TMR iso ), and maximum heat flow ( Q max ) were estimated to ascertain the degree of thermal hazard under various transportation and storage temperatures. The Heat-Wait-Search mode of accelerating rate calorimeter has been used to investigate decomposition kinetics parameters data under an adiabatic condition. Data such as initial exothermic temperature ( T 0 ), self-heating rate (d T/ d t ), pressure rise rate (d P/ d t ) and pressure–temperature profiles help to gauge the runaway reaction hazard of CHP alone and then mixed with its products to support the autocatalytic model of exothermic decomposition. The curve fitting data indicated that activation energy had reduced from 245.4 to 236.7 and 242.3 kJ mol −1 , when CHP was mixed with acetone or dicumyl peroxide, respectively. The decrease in activation energy for autocatalytic material thermal decomposition reaction is depicted here with various experimental findings and mathematical analysis.