Thermal Oscillations in the Decomposition of Organic Peroxides: Identification of a Hazard, Utilization, and Suppression

Abstract

The purpose of this research is to identify and characterise oscillatory thermal instability in organic peroxides that are used in vast quantities in industry and misused by terrorists. The explosive thermal decompositions of lauroyl peroxide, methyl ethyl ketone peroxide and triacetone triperoxide are investigated computationally, using a continuous stirred tank reactor model and literature values of the kinetic and thermal parameters. Mathematical stability analysis is used to identify and track the oscillatory instability, which may be violent. In the mild oscillatory regime it is shown that, in principle, the oscillatory thermal signal may be used in microcalorimetry to detect and identify explosives. Stabilization of peroxide thermal decomposition via Endex coupling is investigated. It is usually assumed that initiation of explosive thermal decomposition occurs via classical (Semenov) ignition at a turning point or saddle-node bifurcation, but this work shows that oscillatory ignition is characteristic of thermoreactive liquids and that Semenov theory and purely steady state analyses are inadequate for identifying thermal hazard in such systems. 2

Parametrische Empfindlichkeit einer stark exothermen Reaktion im Kapillarwendelreaktor

“…Beispielsweise wurden von 1953 bis 2007 mehrere Unfälle allein im Umgang mit Methylethylketonperoxid registriert, die zu 102 Toten und 332 Verletzten führten. Sie alle haben ihre Ursache im Durchgehen der Reaktion 3. Deshalb soll diese Arbeit einen Beitrag zur Vereinfachung der Vorhersage von kritischen Reaktionsbedingungen leisten.…”

Transition from Thermokinetic to Chemical Instabilities in a Modified Sal’nikov Model

“…It has been known for years that thermal oscillations occur in chemical reactions, with autocatalysis as a source of instability, in both isothermal reactors and adiabatic reactors, 16,17,31 the same type of oscillations occur in chemical processes that are known to be thermokinetically unstable. [4][5][6][7] Both kinds of oscillatory behavior (thermal and chemical) have been shown in this paper using a feasible dynamic model, which we have called the Sal'nikov unified model (see equations [8][9][10].…”

“…15,16 These oscillations are particularly relevant in cases where uncontrolled temperature increases represent a security risk, since thermal runaway development could be a lethal hazard. 17 Additionally, several examples of thermal oscillatory behavior can be found in combustion reactions, traditionally modeled as the Sal'nikov thermokinetic oscillator. [4][5][6][7] According to the mechanism of the model, the Sal'nikov oscillator is driven only by temperature changes, and is said to be a pure thermal oscillator.…”

The application of dynamic modeling for thermal risks analysis of the acid‐catalyzed hydrolysis of glycidol

“…As a result, many series of recommendations and safety regulations have been implemented to prevent poor process procedures and to reduce risks . Parametric sensitivity and dynamic analyses have been developed as tools for hazard process assessment . Thus, the parametric sensitivity analysis allows identifying temperature maxima (hot spots) into the reactor and runaway criteria; while the dynamic one lets to track thermal stability, showing how the thermal behavior is changing under the variations of different operational parameters .…”