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Exothermic behaviors in decomposition of three solid organic peroxides by DSC and VSP2

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Abstract

The decomposition of organic peroxides by their relatively weak oxygen linkage and hydroperoxide radical in the presence of reaction solution is one of the thermal hazards for triggering a runaway reaction. Runaway incidents may occur in oxidation reactors, vacuum condensation reactors, tank lorries, or storage tanks. In NFPA 432 organic peroxides in NFPA 432 are classified as flammable. The exothermic behaviors of solid organic peroxides, dicumene peroxide, benzoyl peroxide, and lauroyl peroxide, were determined by differential scanning calorimetry (DSC), and vent sizing package 2 (VSP2). Relevant data detected by DSC provided thermal stability information, such as exothermic onset temperature (T 0), maximum heat-releasing peak (T max), and heat of decomposition (ΔH d). VSP2 was used to perform the bench scale situation for pushing the expected or unexpected reaction to undergo runaway reaction. Onset temperature, maximum pressure, self-heating rate ((dT dt −1)max), and pressure-release rate ((dP dt −1)max) were therefore obtained and explained. These results are essentially crucial in process design for an inherently safer approach.

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Acknowledgements

The authors are indebted to the donors of the National Science Council (NSC) in Taiwan under the contract number NSC-99-2221-E-224-029-MY3 for financial support.

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Authors and Affiliations

  1. Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, 200, Xiao Ling Wei Street, Nanjing, 210094, China, PRC

    Lung-Chang Tsai

  2. Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC

    Jyun-Wei Chen, Shang-Hao Liu & Chi-Min Shu

  3. Department of Occupational Safety and Health, Jen-Teh Junior College of Medicine, Nursing and Management, 1, Jen-Teh Rd., Houlong, Miaoli, 35665, Taiwan, ROC

    Hung-Yi Hou

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  1. Lung-Chang Tsai
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  2. Jyun-Wei Chen
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  5. Chi-Min Shu
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Correspondence to Chi-Min Shu.

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Tsai, LC., Chen, JW., Hou, HY. et al. Exothermic behaviors in decomposition of three solid organic peroxides by DSC and VSP2. J Therm Anal Calorim 109, 1303–1309 (2012). https://doi.org/10.1007/s10973-012-2520-2

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