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Isothermal and non-isothermal calorimetric techniques combined with a simulation approach for studying the decomposition characteristics of di(2,4-dichlorobenzoyl) peroxide

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Abstract

Disasters caused by organic peroxides, such as di(2,4-dichlorobenzoyl) peroxide (DCBP), are mainly attributed to the presence of unstable oxygen atom bonds. In this study, DCBP was investigated through differential scanning calorimetry and thermal activity monitor III, which yielded thermokinetic data to delve into the pure decomposition characteristics of DCBP undergoing chemical reactions. In addition, the thermokinetic data were used to determine the thermal safety parameters through simulation using a best-fit approach based on an appropriately chosen kinetic model and thermal safety software. We found that DCBP decomposes more satisfactorily by an autocatalytic reaction at low temperatures. The apparent activation energy determined through various approaches, such as Kissinger and Ozawa methods, and thermal safety software simulation were studied. Although DCBP decomposition deposits with dioxins, which require major decontamination measures, DCBP is used to produce silicone products globally. The present study establishes threshold thermokinetic parameters for packing and handling thermally sensitive organic peroxides; these thresholds help predict unwarranted runaway reactions, which entail enormous pressure rise and release of toxic by-products to the environment.

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Abbreviations

A :

Frequency factor of reaction (s−1 M1−n)

E a :

Apparent activation energy (kJ mol−1)

ΔH d :

Heat of decomposition (J g−1)

k 0 :

Pre-exponential factor (s−1)

k iso :

Reaction rate constant under isothermal conditions (h)

n :

Reaction order (dimensionless)

n i :

Reaction order of ith stage (dimensionless)

Q :

Heat production (kJ kg−1)

R :

Universal gas constant (8.314 J mol−1 K−1)

T :

Absolute temperature (K)

T max :

Maximum temperature of reaction (°C or K)

TMR iso :

Time to maximum rate under isothermal conditions (h)

T o :

Apparent exothermic onset temperature of reaction (°C)

W p :

Highest heat flow at time t (w g−1)

z :

Autocatalytic constant (dimensionless)

α :

Degree of conversion (dimensionless)

β :

Heating rate (°C min−1)

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Acknowledgements

We express our appreciation to the members at Process Safety and Disaster Prevention Laboratory for the experimental support and research assistance. We are grateful to Dr. Kuang-Hua Hsueh for his expert opinions. We also appreciate Ms. Tzu-Hao Lin and Mr. Shih-Yu Huang for experimental assistance.

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Authors and Affiliations

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

    Ming-Hsun Lee & Bin Laiwang

  2. Department of Industrial Engineering and Management, Hsiuping University of Science and Technology (HUST), 11, Gong-Ye Rd., Dali, 41280, Taichung, Taiwan

    Ming-Hsun Lee & Jiann-Rong Chen

  3. Department of General Education Center, Chienkuo Technology University, No. 1, Chieh Shou N. Rd., Changhua, 50094, Taiwan

    Mei-Li You

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  1. Ming-Hsun Lee
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Correspondence to Jiann-Rong Chen.

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Lee, MH., You, ML., Laiwang, B. et al. Isothermal and non-isothermal calorimetric techniques combined with a simulation approach for studying the decomposition characteristics of di(2,4-dichlorobenzoyl) peroxide. J Therm Anal Calorim 127, 1099–1106 (2017). https://doi.org/10.1007/s10973-016-5973-x

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