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Kinetic modeling for thermal hazard of 2,2′-azobis (2-methylpropionamide) dihydrochloride using calorimetric approach and simulation

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Abstract

Azo compounds are usually used as initiators and blowing agents. They are also typically self-reactive materials capable of undergoing a runaway reaction during storage or transportation, which can cause serious fires and explosions. To prevent the thermal hazard of azos occurring in a real process, transportation, or storage, azo initiator 2,2′-azobis (2-methylpropionamide) dihydrochloride (AIBA), which has few studies on relevant research in thermal safety, was selected to be investigated. First, the features of thermal decomposition under non-isothermal condition of AIBA were attained through differential scanning calorimetry and simultaneous thermal analysis. Second, the collected data were substituted into mathematical analyzer to evaluate the basic thermal hazard for AIBA. In addition, based on Semenov theoretical model and thermokinetic parameters, the critical ignition temperature (TCI) was extrapolated for consideration of surroundings temperature under specific cooling system (TS). The results provided process control data and the consequences of thermal runaway for AIBA. In addition, the related numerical methods for prevention of thermal runaway reaction could be calculated during process deviation. Therefore, the assessment conclusions also showed that process parameters must be measured and controlled strictly to generate the desired reaction. The results showed that the various TCI were all less than 70 °C. Therefore, it is essential to avoid a temperature beyond the TCI or cooling system failure.

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Abbreviations

R :

Gas constant/8.31415 J K−1 mol−1

A :

Pre-exponential factor of Arrhenius equation (min−1)

A(α):

Pre-exponential factor at conversion (min−1)

A′(α):

Amended pre-exponential factor by a product of \(A (\alpha )\) and \(f (\alpha )\) (min−1)

C o :

Original concentration of the material (g cm−3)

C :

Concentration of the material (g cm−3)

C p :

Specific heat of material (J g−1 K−1)

E a :

Apparent activation energy (kJ mol−1)

E(α):

Apparent activation energy factor at conversion (kJ mol−1)

h :

Heat exchange capability index of the cooling system (kJ m−2 K−1 min−1)

k 0 :

Reaction rate constant (s−1)

n :

Reaction order (dimensionless)

m :

Mass of material (g)

ΔH d :

Heat of decomposition (J g−1)

ΔH t :

Heat of decomposition at time (J g−1)

ΔH total :

Total heat of decomposition (J g−1)

r :

Reaction rate (s−1)

q g :

Heat production rate (kJ min−1)

q r :

Heat removal rate (kJ min−1)

q r1 :

Heat removal rate by high cooling medium (kJ min−1)

q r2 :

Heat removal rate by cooling system (kJ min−1)

q r3 :

Heat removal rate by low cooling system (kJ min−1)

S :

Effective heat exchange area (m2)

V :

Volume of process instruments (m3)

T :

Process temperature (K)

T 0 :

Apparent exothermic temperature (K)

T P :

Temperature at the maximum heat release in reaction (K)

T S :

Surrounding temperature under cooling system (K)

t :

Reaction time (min)

T CI :

Critical ignition or extinction temperature (K)

T CE :

Critical extinguishing temperature (K)

T SE :

Stable point of extinguishing temperature (K)

TSI :

Stable point of ignition temperature (K)

T SL :

Stable point at lower temperature (K)

T SH :

Stable point at higher temperature (K)

T M :

Cutoff point between curves qg and qr at the highest and lowest cooling efficient system (K)

X A :

Fractional conversion (dimensionless)

α :

Degree of conversion (dimensionless)

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Acknowledgements

The authors wish to express their gratitude to Dr. Arcady A. Kossoy of ChemInform Saint Petersburg, Federation, Russian, for providing technical assistance. The authors would also like to thank Dr. Shang-Hao Liu and Dr. Kuo-Ming Luo for their help on the measurements of critical parameters.

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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, ROC

    Chen-Rui Cao

  2. Department of Safety, Health, and Environment Engineering, YunTech, 123, University Rd., Sec. 3, Douliou, 64002, Yunlin, Taiwan, ROC

    Chi-Min Shu

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Correspondence to Chi-Min Shu.

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Cao, CR., Shu, CM. Kinetic modeling for thermal hazard of 2,2′-azobis (2-methylpropionamide) dihydrochloride using calorimetric approach and simulation. J Therm Anal Calorim 137, 1021–1030 (2019). https://doi.org/10.1007/s10973-018-07995-8

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  • DOI: https://doi.org/10.1007/s10973-018-07995-8

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