Further explanations of lauroyl peroxide runaway reaction by DSC tests and simulations

It is our honor and pleasure to discuss some phenomena of specific organic peroxide with Prof. M. Malow and Prof. K. D. Wehrstedt. The kinetic parameters of the thermal behavior of lauroyl peroxide (LPO) were detected by DSC under nonisothermal conditions. Kinetic models and algorithms for thermal analysis were invented by Kossoy, Akhmetshin, and their associates (2007) of the Thermal Safety Software (TSS) [1–6]. Inputting experimentally derived data of interest into TSS is a simple analytical process that can be used to estimate or predict the thermal hazard of organic peroxides and other energetically sensitive materials to achieve optimization in the safety approaches of chemical plants. In our laboratory, many applied cases [7–10] in the use of organic peroxides and energetic materials have already been studied using this method. For instance, from Tables 1 and 2, the kinetic parameters of the thermal behavior of LPO were tested by DSC in non-isothermal conditions (with heating rates of 1, 2, 4, and 10 C min) first. Then they were further simulated using TSS by nth order and autocatalytic reaction processes, respectively. In addition, the thermal hazard parameters of LPO, time to maximum rate (TMR), and a certain time to conversion limit (TCL) at heating rates of 1, 2, 4, and 10 C min by nth order and autocatalytic simulation were shown in Figs. 1 (for TMR) and 2 (for TCL). Under adiabatic condition, TMR is normally employed as a critical index of a temperature with an explosive accident potential once over by the surrounding temperature. According to Fig. 1, through simulation of a temperature of 70 C, the TMR value was about 3–5 min. Utilization of this data could enable an operator to know how much time would be available for emergency response in the event of a runaway reaction. LPO is solid organic peroxide, belonging to the group of quasi-autocatalytic reactions of thermal decomposition [11]. When LPO was stored under isothermal conditions, over a long time, an abrupt self-heating of the resultant liquid started. In essence, exothermic decomposition reactions can begin when the solid and liquid phases coexist on one container [12]. Another parameter for determining thermal stability, which is characterized by the time necessary to reach TCL, was necessary to determine the stability of materials under storage or transportation conditions. In our previous studies associated with the aforementioned kinetic-based simulation approach, three main steps were conducted: executing a necessary series of calorimetric experiments; building up the mathematical model of a reaction based on experimental data of DSC, incorporating the kinetic model into the model of processing; and achieving the practical target by applying mathematical simulations. In case of a package containing a solid with both internal heat losses from the surface are important [6]. Various vessel types with different material densities were chosen for simulation, like LPO in box is simulated by solid thermal explosion specifying boundary conditions of the first, second, and third type. Transport package sizes and boundary conditions, shown in Tables 3 and 4, were assumed to be uniform over each package’s surface. M.-L. You Department of General Education Center, Chienkuo Technology University, 1, Chieh-Shou N. Rd., Changhua 50094, Taiwan ROC