Safe operation of a batch reactor: Safe storage of organic peroxides in supply vessels

Abstract

In this study, we investigated the limits of safe operation for a cooled reactor, operated batchwise. As an example of a single-phase reaction, we studied the decomposition of t-butyl peroxypivalate, a well-known organic peroxide, undergoing self-heating at relatively low temperatures. If sufficiently diluted, it can be supplied to a polymerization process from large, cooled but unstirred vessels. We present a number of extensions to the existing homogeneous explosion theory, namely a practical definition of the critical condition, its calculation, and expressions for the available time before runaway in the case of a supercritical condition, taking into account the effects of natural convection inside the vessel and the reactant conversion. The extensions of the theory were confirmed by adiabatic and non-adiabatic runaway experiments on bench scale, and natural convection cooling experiments with liquids in various packages.

On the occurrence of thermal explosion in a reacting gas: The effects of natural convection and consumption of reactant

“…Consequently, the condition that ' T = 2 for a first-order reaction exploding may no longer be appropriate. This assertion has been supported by Steensma and Westerterp [34], who suggested a value of ' T = 5 to define an explosion, rather than ' T = 2.…”

Evaluation of the validity of the UN SADT H.4 test for solid organic peroxides and self-reactive substances

“…The resulting T cr from equation (2) is rather insensitive, at most a few degrees K, to factors such as varying specific heat, order of the reaction, total heat of reaction and activation energy, according to [7]. Surprisingly, equation (2) does not contain the parameter time, but by calculation the practical definition of the criticality in the UN SADT test (temperature excursion of 6 K after 7 days) gives a T cr very close to the outcome of equation (2).…”

“…A complicated, but still approximate solution is derived in [7], from which the following expression for the critical condition can be derived:…”

Calorimetric study of peroxycarboxylic ester synthesis

“…[7][8][9][10]) and of peroxycarboxylic esters in particular (e.g. [11][12][13][14][15]). Publications concerning heat production of synthesis are rare in the public literature.…”