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Prediction of thermal hazard of liquid organic peroxides by non-isothermal and isothermal kinetic model of DSC tests

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Abstract

Liquid organic peroxides (LOPs) have been widely used as initiators of polymerization, hardening, or cross-linking agents. We evaluated a beneficial kinetic model to acquire accurate thermokinetic parameters to help preventing runaway reactions, fires or explosions in the process environment. Differential scanning calorimetry was used to assess the kinetic parameters, such as kinetic model, reaction order, heat of reaction (ΔH d), activation energy (E a), frequency factor (lnk 0), etc. The non-isothermal and isothermal kinetic models were compared to determine the validity of the kinetic model, and then applied to the thermal hazard assessment of commercial package contaminated with LOPs. Simulations of a 0.5-L Dewar vessel and 25-kg commercial package were performed. We focused on the thermal stability of different liquid system properties for LOPs. From the results, the optimal conditions were determined for avoiding violent heat effects that can cause a runaway reaction in storage, transportation, and manufacturing.

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Abbreviations

CP :

Specific heat capacity (J g−1 K−1)

CT:

Control temperature (°C)

E a :

Activation energy (kJ mol−1)

E 1 :

Activation energy of the 1st stage (kJ mol−1)

E 2 :

Activation energy of the 2nd stage (kJ mol−1)

ET:

Emergency temperature (°C)

f i :

Kinetic functions of the ith stage i = 1, 2, 3

f(α):

Kinetic functions

k 0 :

Pre-exponential factor (m3 mol−1 s−1)

k i :

Reaction rate constant (mol L−1 s−1) i = 1, 2

n :

Reaction order or unit outer normal on the boundary, dimensionless

NC:

Number of components, dimensionless

n i :

Reaction order of the ith stage, dimensionless i = 1, 2, 3

Q ∞ i :

Specific heat effect of a reaction (J kg−1)

q :

Heat flow (J g−1)

R :

Gas constant (8.31415 J K−1 mol−1)

r i :

Reaction rate of the ith stage (g sec−1) i = 1, 2, 3, 4

S :

Heat-exchange surface (m2)

SADT:

Self-accelerating decomposition temperature (°C)

T :

Absolute temperature (K)

T 0 :

Exothermic onset temperature (°C)

TCL:

Time to conversion limit (year)

TCR:

Critical temperature (°C)

TER:

Total energy release (kJ kg−1)

T e :

Ambient temperature (°C)

TMRiso :

Time to maximum rate under isothermal conditions (day)

T wall :

Temperature on the wall (°C)

t :

Time (sec)

W :

Heat power (W g−1)

z :

Autocatalytic constant, dimensionless

α:

Degree of conversion, dimensionless

γ:

Degree of conversion, dimensionless

ρ:

Density (kg m−3)

λ:

Heat conductivity (W m−1 K−1)

χ:

Heat transfer coefficient (W m−2 K−1)

∆H d :

Heat of decomposition (kJ kg−1)

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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 100-2218-E-468-001- for financial support. In addition, the authors are grateful to ACE Chemical Corp. Taiwan, ROC.

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Authors and Affiliations

  1. Institute of Safety and Disaster Prevention Technology, Central Taiwan University of Science and Technology, 666, Buzih Rd., Taichung, 40601, Taiwan, ROC

    Jo-Ming Tseng

  2. General Education Center, Chienkuo Technology University, 1, Chieh Shou N. Rd., Changhua, 50094, Taiwan, ROC

    Tung-Feng Hsieh & Yi-Ming Chang

  3. Department of Emergency and Resources, National United University, 1, Lienda Rd., Miaoli, 36003, Taiwan, ROC

    Lu-Yen Chen

  4. Department of Health and Nutrition Biotechnology, Asia University, 500, Lioufeng Rd., Wufeng, Taichung, 41354, Taiwan, ROC

    Ya-Chen Yang & Chun-Ping Lin

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  1. Jo-Ming Tseng
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  2. Tung-Feng Hsieh
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  3. Yi-Ming Chang
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  4. Ya-Chen Yang
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Correspondence to Chun-Ping Lin.

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Tseng, JM., Hsieh, TF., Chang, YM. et al. Prediction of thermal hazard of liquid organic peroxides by non-isothermal and isothermal kinetic model of DSC tests. J Therm Anal Calorim 109, 1095–1103 (2012). https://doi.org/10.1007/s10973-011-2125-1

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