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Thermal hazard analyses of organic peroxides and inorganic peroxides by calorimetric approaches

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Abstract

Organic peroxides (OPs) and inorganic peroxides (IPs) are usually employed as an initiator for polymerization, a source of free radicals, a hardener, and a linking agent in low density polyethylene (LDPE), polyvinyl chloride (PVC), controlled-rheology polypropylene (CR-PP), and styrene industries. Worldwide, due to their unstably reactive natures, OPs and IPs have caused many serious thermal explosions and runaway reaction incidents. This study was conducted to elucidate its essentially hazardous characteristics. To analyze the runaway behavior of OPs and IPs in the traditional process, thermokinetic parameters including heat of decomposition (ΔH d ), exothermic onset temperature (T 0), self-accelerating decomposition temperature (SADT), time to maximum rate (TMR), critical temperature (T c ), etc., were measured by calorimetric approaches involving differential scanning calorimetry (DSC), vent sizing package 2 (VSP2), and calculation method. Safety and health handling information of hazardous materials and toxic substances is noted in material safety data sheets (MSDS) and was applied to analyze in process safety management (PSM) in the chemical industries, but MSDS are not providing important handling indicators concerning the SADT, TMR, T c , etc. In view of loss prevention, more useful indicators must be provided in the sheets or guide book.

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Abbreviations

A :

Frequency factor, sec−1 M1–n

C p :

Liquid specific heat at constant pressure, kJ kg−1 °C−1

C 0 :

Initial concentration, mol L−1

E a :

Activation energy, kJ mol−1

K :

Pre-exponential factor, s−1

M :

Mass of reactant, g

P max :

Maximum pressure during overall reaction, psig

Q :

Calorific capacity, J g−1.

\( \mathop Q\limits^{ \bullet } \) :

heat flow, W g−1

R :

Gas constant, 8.314 J mol−1 K−1

S :

Wetted surface area, m2

SADT:

Self-accelerating decomposition temperature, °C

T :

Temperature, °C

T A :

Final adjusted temperature, K

T A0 :

Initial adjusted temperature, K

T f :

Final temperature, °C

T M :

Final measured temperature, K

T max :

Maximum temperature during overall reaction, °C

T M0 :

Initial measured temperature, K

T NR :

Temperature of no return, °C

T wall :

Temperature on the wall, °C

TMRad :

Time to maximum rate under adiabatic system, min, h

U :

Heat transfer coefficient, kJ min−1 m−2 K−1

a :

Vessel wetted surface area, m2

k i :

Rate at stage i, s−1

m :

Mass of reactor, kg

n :

Order of reaction, dimensionless

α:

Degree of conversion, dimensionless

β:

Heating rate, °C min−1

λ:

Heat conductivity, J ms K−1

\( \varphi \) :

Thermal inertia, dimensionless

∆H d :

Heat of decomposition, J g−1

(dT dt −1):

Self-heating rate, °C min−1

(dT dt −1)A :

Actual self-heating rate, °C min−1

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Authors and Affiliations

  1. Department of Fire Science, WuFeng University, 117, Chian-Kuo Rd., Sec. 2, Min-Hsiung, Chiayi, 62153, Taiwan, ROC

    Sheng-Hung Wu & Jen-Hao Chi

  2. Department of Disaster Management, Taiwan Police College, 153 Shing-Lung Rd., Sec. 3, Taipei, 11696, Taiwan, ROC

    Hung-Cheng Chou & Ryh-Nan Pan

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

    Yi-Hao Huang, Jao-Jia Horng & Chi-Min Shu

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  1. Sheng-Hung Wu
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Correspondence to Sheng-Hung Wu.

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Wu, SH., Chou, HC., Pan, RN. et al. Thermal hazard analyses of organic peroxides and inorganic peroxides by calorimetric approaches. J Therm Anal Calorim 109, 355–364 (2012). https://doi.org/10.1007/s10973-011-1749-5

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  • DOI: https://doi.org/10.1007/s10973-011-1749-5

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