Sensitivity-based Runaway Criteria

A more recent class of criteria to identify runaway conditions is based on the evidence that, close to runaway boundaries, the system behavior becomes highly sensitive to even small changes of the model parameters. Within this class, the generalized criterion of Morbidelli and Varma [14] makes use of the absolute value of the normalized objective sensitivity s of the temperature maximum 7 max to the generic model parameter 0, defined as... 

In Fig. 11.5.C-2 the locus of the partial pressure and temperature in the maximum of the temperature profile and the locus of the inflection points before the hot spot are shown as p and (pj), respectively. Two criteria were derived from this. The first criterion is based on the observation that extreme sensitivity is found for trajectories—the p-T relations in the reactor—intersecting the maxima curve p beyond its maximum. Therefore, the trajectory going through the maximum of the p -curve is considered as critical. This is a criterion for runaway based on an intrinsic property of the system, not on an arbitrarily limited temperature increase. The second criterion states that runaway will occur when a trajectory intersects (Pi)i, which is the locus of inflection points arising before the maximum. Therefore, the critical trajectory is tangent to the (pi)i-curve. A more convenient version of this criterion is based on an approximation for this locus represented by p in... 

Following the Morbidelli and Varma criterion, several other methods have been proposed in recent years in order to characterize the highly sensitive behavior of a batch reactor when it reaches the runaway boundaries. Among the most successful approaches, the evidence of a volume expansion in the phase space of the system has been widely exploited to characterize runaway conditions. For example, Strozzi and Zaldivar [9] defined the sensitivity as a function of the sum of the time-dependent Lyapunov exponents of the system and the runaway boundaries as the conditions that maximize or minimize this Lyapunov sensitivity. This has put the basis for the development of a new class of runaway criteria referred to as divergence-based approaches [5,10,18]. These methods usually identify runaway with the occurrence of a positive divergence of the vector field associated with the mathematical model of the reactor. 

Bilous and Amundson [1] were the first to describe the phenomenon of parametric sensitivity in cooled tubular reactors. This parametric sensitivity was used by Barkelew [2] to develop design criteria for cooled tubular reactors in which first order, second order and product- inhibited reactions take place. He presented diagrams from which for a certain tube diameter dt the required combination of CAO and Tc can be derived to avoid runaway or vice versa. Later van Welsenaere and Froment [3] did the same for first order reactions, but they also used the inflexion points in the reactor temperature T versus relative conversion XA trajectories, which describe the course of the reaction in the tubular reactor. With these trajectories they derived a less conservative criterion. Morbidelli and Varma [4] recently devised a method for single order reactions based on the isoclines in a temperature conversion plot as proposed by Oroskar and Stern [5]. 

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