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Thermal risk assessment and rankings for reaction hazards in process safety

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Abstract

Reaction hazards remain the most serious concern in the chemical industry in spite of continual research and attention devoted to them. Many commercial calorimeters, such as the Differential Scanning Calorimetry (DSC), are useful screening tools for thermal risk assessment of reaction hazards. Some important thermodynamic and kinetic parameters, including onset temperature, adiabatic time to maximum rate, and maximum adiabatic temperature, were analyzed in this paper. A kinetic-based model under adiabatic conditions was developed, and the adiabatic time to maximum rate was estimated. Correlations between onset temperature (T o) and activation energy (E a), and between onset temperature (T o) and adiabatic time to maximum rate (TMR ad) were found, and were illustrated by some examples from the previous literature. Based on the heat of reaction and the adiabatic time to maximum rate, a thermal risk index (TRI) was defined to represent the thermal risk of a specific reaction hazard relative to di-tert-butyl peroxide (DTBP), and the results of this index were consistent with those of the reaction hazard index (RHI). The correlations and the thermal risk index method could be used as a preliminary thermal risk assessment for reaction hazards.

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Abbreviations

A 0 :

Pre-exponential factor

BDE:

Bond dissociation energy

C A :

Concentration (mol/m3)

C p :

Specific heat capacity (J/kg∙K)

C pc :

Specific heat capacity of container (J/kg∙K)

C′p :

Specific heat capacity (J/mol∙K)

DSC:

Differential Scanning Calorimetry

DTBP:

Di-tert-butyl peroxide

E a :

Activation energy (kJ/mol or kcal/mol)

h :

Planck’s constant (J∙s)

−ΔH r :

Heat of reaction (kJ/mol or cal/g)

k :

Rate constant (1/s)

k B :

Boltzmann’s constant (J/K)

m :

Mass of chemical sample (kg)

m c :

Mass of container (kg)

\( \dot{q} \) :

Heat release rate at any temperature (W/kg)

\( \dot{q}_{\text{o}} \) :

Heat release rate at T o (W/kg)

R :

Gas constant (J/mol∙K)

r A :

Reaction rate (mol/m3·s)

RHI:

Reaction hazard index

t :

Time (s or min)

T :

Absolute temperature (K)

TBPA:

t-Butyl peroxy acetate

T m :

Maximum adiabatic decomposition temperature (K)

TMR ad :

Time to maximum rate at adiabatic conditions (s or min)

T o :

Onset temperature where the heat release rate is 0.1 °C/min (K)

TRI:

Thermal risk index

V :

Reaction volume (m3)

β :

Ratio of consequence

γ p :

Transfer coefficient

\( \varepsilon \) :

Ratio of probability

Φ :

Thermal inertia coefficient

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Acknowledgements

This research was supported by the Mary Kay O’Connor Process Safety Center (MKOPSC) and Artie McFerrin Department of Chemical Engineering at Texas A&M University.

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Authors and Affiliations

  1. Mary Kay O’Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX, 77843-3122, USA

    Qingsheng Wang, William J. Rogers & M. Sam Mannan

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  1. Qingsheng Wang
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  2. William J. Rogers
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  3. M. Sam Mannan
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Correspondence to M. Sam Mannan.

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Wang, Q., Rogers, W.J. & Mannan, M.S. Thermal risk assessment and rankings for reaction hazards in process safety. J Therm Anal Calorim 98, 225–233 (2009). https://doi.org/10.1007/s10973-009-0135-z

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  • DOI: https://doi.org/10.1007/s10973-009-0135-z

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