Runaway reactor condition

Even when there are no disturbances in the feed or in the reactor conditions, a cooled CSTR may still show some instability. This has been studied extensively by Fortuin and coworkers, who found that sustained oscillations or limit cycles may occur. Apparently there exist several possible steady states, that all satisfy eq. (8.8). It may happen that the reactor temperature and the conversion oscillate between two steady states. Under particular conditions, a slight disturbance may be magnified, resulting either in a runaway or in complete extinction of the reaction. Several of these phenomena were demonstrated both by simulation and by real experiments (Vermeulen and Fortuin, 1986, Vleeschhouwer and Fortuin, 1990). 

The maximum attainable production was sought that did not cause thermal runaway. By gradually increasing the temperature of the water, boiling under pressure in the reactor jacket, the condition was found for the incipient onset of thermal instability. Runaway set in at 485.2 to 485.5 K for the 12 m reactor and at 435.0 to 435.5 K for the shorter, 1.2 m reactor. The smaller reactor reached its maximum operation limit at 50 K lower than the larger reactor. The large reactor produced 33 times more methanol, instead of the 10 times more expected from the sizes. This... 

The unit was built in a loop because the needed 85 standard m /hour gas exceeded the laboratory capabilities. In addition, by controlling the recycle loop-to-makeup ratio, various quantities of product could be fed for the experiments. The adiabatic reactor was a 1.8 m long, 7.5 cm diameter stainless steel pipe (3 sch. 40 pipe) with thermocouples at every 5 centimeter distance. After a SS was reached at the desired condition, the bypass valve around the preheater was suddenly closed, forcing all the gas through the preheater. This generated a step change increase in the feed temperature that started the runaway. The 20 thermocouples were displayed on an oscilloscope to see the transient changes. This was also recorded on a videotape to play back later for detailed observation. 

Some batch reactions have the potential for very high energy levels. If all the reactants (and sometimes catalysts) are put into a kettle before the reaction is initiated, some exothermic reactions may result in a runaway. The use of continuous or semi-batch reactors to limit the energy present and to reduce the risk of a runaway should be considered. The term semi-batch refers to a system where one reactant and, if necessary, a catalyst is initially charged to a batch reactor. A second reactant is subsequently fed to the reactor under conditions such that an upset in reacting conditions can be detected and the flow of the reactant stopped, thus limiting the total amount of potential energy in the reactor. 

To do this we developed a computer model to predict the kinetic conditions during the runaway stage. The kinetic model is used to estimate the reaction rates, temperatures, pressures, viscosities, conversions, and other variables which influence reactor design. 

Finally, the oxidation reaction has to been run under strict conditions of temperature, which are impossible to be operated in a batch reactor. Indeed, utility stream in the Shimtec reactor was heated to 47 °C, which first initiates the reaction, accelerates its kinetics, and then controls the temperature when the heat of the reaction is too important. In a batch reactor, working with such UF temperature is impossible because of security constraints. It would certainly lead to a reaction runaway. We now consider this question in the next section. 

Since the generation rate is exponential whereas the removal rate is linear, for any exothermic reaction in a specific reactor configuration a critical condition may exist, i.e. a value of beyond which runaway occurs. 

Sebastian, D. H. et al., Polym. Eng. Sci., 1976, 16, 117-123 The conditions were determined for runaway/non-runaway polymerisation of styrene in an oil-heated batch reactor at 3 bar, using dibenzoyl peroxide as initiator at 3 concentrations. Results are presented diagrammatically. 

Moderate (attenuation and limitation of effects) Use vacuum to reduce boiling point Reduce process temperatures and pressures Refrigerate storage vessels Dissolve hazardous material in safe solvent Operate at conditions where reactor runaway is not possible Place control rooms away from operations Separate pump rooms from other rooms Acoustically insulate noisy lines and equipment Barricade control rooms and tanks... 

Table 3.5 shows that the study of chemical kinetics is critical in successful scale-up of catalytic systems, of gas-phase controlled systems, and of continuous tank stirred reactors (CSTR). For scale-up of batch systems consisting of gas or liquid compounds, chemical kinetics and heat transfer effects must be studied because the combination of these phenomenon determine the conditions for a runaway and thus involve the safety of the operation. 

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