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Abstract  

Lauroyl peroxide (LPO) is a typical organic peroxide that has caused many thermal runaway reactions and explosions. Differential scanning calorimetry (DSC) was employed to determine the fundamental thermokinetic parameters that involved exothermic onset temperature (T0), heat of decomposition (ΔHd), and other safety parameters for loss prevention of runaway reactions and thermal explosions. Frequency factor (A) and activation energy (Ea) were calculated by Kissinger model, Ozawa equation, and thermal safety software (TSS) series via DSC experimental data. Liquid thermal explosion (LTE) by TSS was employed to simulate the thermal explosion development for various types of storage tank. In view of loss prevention, calorimetric application and model analysis to integrate thermal hazard development were necessary and useful for inherently safer design.

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Abstract  

Organic peroxides have caused many serious explosions and fires that were promoted by thermal instability, chemical pollutants, and even mechanical shock. Cumene hydroperoxide (CHP) has been employed in polymerization and for producing phenol and dicumyl peroxide (DCPO). Differential scanning calorimetry (DSC) has been used to assess the thermal hazards associated with CHP contacting sodium hydroxide (NaOH). Thermokinetic parameters, such as exothermic onset temperature (T 0), peak temperature (T max), and enthalpy (ΔH) were obtained. Experimental data were obtained using DSC and curve fitting using thermal safety software (TSS) was employed to obtain the kinetic parameters. Isothermal microcalorimetry (thermal activity monitor, TAM) was used to investigate the thermal hazards associated with storing of CHP and CHP mixed with NaOH under isothermal conditions. TAM showed that in the temperature range from 70 to 90°C an autocatalytic reaction occurs. This was apparent in the thermal curves. Depending on the operating conditions, NaOH may be one of the chemicals or catalysts incompatible with CHP. When CHP was mixed with NaOH, the T 0 is lower and reactions become more complex than those associated with assessment of the decomposition of the pure peroxide. The data by curve fitting indicated that the activation energy (E a) for the induced decomposition is smaller than that for decomposition of CHP in the absence of hydroxide.

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Abstract  

Dicumyl peroxide (DCPO) is usually employed as an initiator for polymerization, a source of free radicals, a hardener, and a linking agent. In Asia, due to its unstable reactive nature, DCPO has caused many thermal explosions and runaway reaction incidents in the manufacturing process. This study was conducted to elucidate its essentially thermal hazard characteristics. In order to analyze the runaway behavior of DCPO in a batch reactor, thermokinetic parameters, such as heat of decomposition (ΔH d) and exothermic onset temperature (T 0), were measured via differential scanning calorimetry (DSC). Thermal runaway phenomena were then thoroughly investigated by DSC. The thermokinetics of DCPO mixed with acids or bases were determined by DSC, and the experimental data were compared with kinetics-based curve fitting of thermal safety software (TSS). Solid thermal explosion (STE) and liquid thermal explosion (LTE) simulations of TSS were applied to determine the fundamental thermal explosion behavior in large tanks or drums. Results from curve fitting indicated that all of the acids or bases could induce exothermic reactions at even an earlier stage of the experiments. In order to diminish the extent of hazard, hazard information must be provided to the manufacturing process. Thermal hazard of DCPO mixed with nitric acid (HNO3) was more dangerous than with other acids including sulfuric acid (H2SO4), phosphoric acid (H3PO4), and hydrochloric acid (HCl). By DSC, T 0, heat of decomposition (ΔH d), and activation energy (E a) of DCPO mixed with HNO3 were calculated to be 70 °C, 911 J g−1, and 33 kJ mol−1, respectively.

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-isothermal 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

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was applied to evaluate for large-scale reactive materials by means of applying a model of the calorimetric technique to evaluate the fundamental exothermic behavior of small-scale ones. The thermal safety software (TSS) package developed by ChemInform

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-009-0592-4 . 16. Thermal safety software (TSS) . St. Petersburg, Russia : ChemInform Saint-Petersburg (CISP) Ltd . http://www.cisp.spb.ru . 17. You , ML , Shu , CM 2011 Further

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