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Thermal risk assessment of tert-butylperoxy-2-ethylhexyl carbonate for storage and transport

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Abstract

Tert-butylperoxy-2-ethylhexyl ester (TBEC) is a typical organic peroxide that is used in pharmaceuticals, materials, intermediates or as a polymerization initiator, and it has a large amount of consumption. We examined the thermal risks of TBEC during storage and transport by using differential scanning calorimetry and thermal activity monitor III to investigate its thermal stability and thermal hazards. Non-isothermal and isothermal experiments were used to calculate the apparent activation energy (E(α)), compare the calculated kinetic data, pre-exponential factor, and other parameters, and infer the thermal behaviour of TBEC under pseudo-adiabatic conditions. According to the calculation results, the E(α) under non-isothermal conditions calculated through the Friedman isothermal kinetic method ranged from 91.47 to 177.35 kJ mol−1. E(α) under isothermal conditions ranged from 157.18 to 143.28 kJ mol−1. TBEC was also tested under pseudo-adiabatic conditions using vent sizing package 2 to investigate uncontrolled thermal runaway. The calculated self-accelerating decomposition temperature was 34.0 °C. Our results provide an insight into the thermal decomposition of TBEC and supply reliable data for its storage and transport processes.

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Abbreviations

A :

Frequency factor (M1–n s−1)

C p :

Specific heat capacity at constant pressure (kJ kg−1 K−1)

E(α):

Apparent activation energy (kJ mol−1)

f(α):

Kinetic function depends on conversions (dimensionless)

(dP/dt)max :

Maximum pressure rise rate (psig min−1)

(dT/dt)max :

Maximum temperature rise rate (°C min−1)

t :

Time (s)

T o :

Exothermic onset temperature (°C or K)

T p1 :

Exothermic peak temperature of the first peak in DSC curves (°C or K)

T p2 :

Exothermic peak temperature of the second peak in DSC curves (°C or K)

SADT :

Self-accelerating decomposition temperature (°C or K)

TMR ad :

Time to maximum rate under pseudo-adiabatic conditions (h or day)

TMR iso :

Time to maximum rate under isothermal conditions (h or day)

α :

Reaction conversion (dimensionless)

β :

Heating rate (°C min−1)

Ф :

Thermal inertia factor (dimensionless)

ΔH d :

Heat of decomposition (J g−1)

W p :

Peak power (W g−1)

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Acknowledgements

The authors are grateful for the financial support of the National Key Research and Development Program (2016YFC0801500), Major Program of the National Natural Science Foundation of China (2143-6006), Major Projects of the Natural Science Research for Colleges in Jiangsu Province (17KJA620002), Priority Academic Program Development of the Jiangsu Higher Education Institutions, and experimental assistance from the Process Safety and Disaster Prevention Laboratory in Taiwan.

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Authors and Affiliations

  1. College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, Jiangsu Province, China

    Chen-Ye Wei, Xu-Hai Pan, Min Hua, Hui-Chun Jiang & Jun-Cheng Jiang

  2. Doctoral Program, Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology (YunTech), 123, University Rd., Sec. 3, Douliou, 64002, Yunlin, Taiwan

    Wei-Cheng Lin

  3. Jiangsu Key Laboratory of Hazardous Chemicals Safety and Control, Nanjing Tech University, Nanjing, 210009, China

    Xu-Hai Pan, Min Hua & Jun-Cheng Jiang

  4. Department of Safety, Health, and Environmental Engineering, YunTech, 123, University Rd., Sec. 3, Douliou, 64002, Yunlin, Taiwan

    Chi-Min Shu

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  1. Chen-Ye Wei
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Wei, CY., Lin, WC., Pan, XH. et al. Thermal risk assessment of tert-butylperoxy-2-ethylhexyl carbonate for storage and transport. J Therm Anal Calorim 138, 2891–2900 (2019). https://doi.org/10.1007/s10973-019-08552-7

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