ABSTRACT
The behavior of thermal explosions or runaway reactions has been widely studied for many years. A reactor with an exothermic reaction is susceptible to accumulating energy and temperature when the heat generation rate exceeds the heat removal rate by Semenov theory (Semenov, 1984). Unsafe actions and behaviors by operators, such as poor training, human error, incorrect kinetic assumptions, insufficient change management, inadequate chemical knowledge etc., lead to runaway reactions, thermal explosions, and release of toxic chemicals, as have sporadically occurred in industrial processes (Smith, 1982). Methyl ethyl ketone peroxide (MEKPO), cumene hydroperoxide (CHP), di-tert-butyl peroxide (DTBP), tert-butyl
peroxide (BPO), hydrogen peroxide (H2O2), lauroyl peroxide (LPO), tert-butyl perbenzoate (TBPBZ), tertbutyl peroxybenzoate (TBPB), etc. are usually applied as initiators and cross-linking agents for polymerization reactions. One reason for accidents involves the peroxy group (-O-O-) of organic peroxides, due to its thermal instability and high sensitivity for thermal sources. The calorimetric technique is applied to evaluate the fundamental exothermic behavior of smallscale reactive materials during the stage of research and development (R&D). Many thermal explosions and runaway reactions have been caused globally by MEKPO resulting in a large number of injuries and even death, as shown in Table 1 (Yeh et al., 2003; Chang et al., 2006; Tseng et al., 2006; Tseng et al., 2007; MHIDAS, 2006). Major Hazard Incident Data
Service (MHIDAS) was employed to investigate three accidents for MEKPO in Australia and UK (MHIDAS, 2006). A thermal explosion and runaway reaction of MEKPO occurred at Taoyuan County (the so-called YungHsin explosion) that killed 10 people and injured 47 in Taiwan in 1996. Figures 1 (a) and 1 (b) show the accident damage situation from the Institute of Occupational Safety and Health in Taiwan.
