Reactor thermal stability

Good heat transfer on the outside of the reactor tube is essential but not sufficient because the heat transfer is limited at low flow rates at the inside film coefficient in the reacting stream. The same holds between catalyst particles and the streaming fluid, as in the case between the fluid and inside tube wall. This is why these reactors frequently exhibit ignition-extinction phenomena and non-reproducibility of results. Laboratory research workers untrained in the field of reactor thermal stability usually observe that the rate is not a continuous function of the temperature, as the Arrhenius relationship predicts, but that a definite minimum temperature is required to start the reaction. This is not a property of the reaction but a characteristic of the given system consisting of a reaction and a particular reactor. 

Figure 3.17 Predicted maximum wall temperatures for t/,N = 10 m/s (filled circles) and L/in = 20 m/s (open circles) versus inlet temperature (Tin) for the CST concept (model in Fig. 3.3) at three different equivalence ratios (A) =0.1, (B) =0.2,and (C) <)j=0.3. Solid triangles provide the computed maximum wall temperatures in the presence of only catalytic reactions at selected cases for (p=02 and 0.3. The adiabatic equilibrium temperatures, Tad, the maximum theoretical wall temperatures, Tv,max-theoiy< from Eq. (3.32) and a limiting wall temperature for reactor thermal stability Tw,iin,it=1500K are also shown. Adapted from Schultze and Mantzaras (2013) (with permission).

Use of thermal stability tests (DTA s) to determine the heat sensitivity of a given process mixture is desirable. Recent advances in analytical methods permit good calorimetric determination of heat of reaction. Heat of reaction data are critical for exothermic reactor vent sizing. Heat impact from fire is usually small in comparison, but should not be neglected. 

The thermal stability of alkali-metal borides is relatively low, which is expected from the high vapor pressures of the corresponding metals at high T. Consequently, the alkali-metal vapor pressure is an important parameter, and synthesis of alkali-metal boride is carried out in isothermal reactors that permit maximum alkali-metal pressure and hence optimum preparation conditions. 

The B-Na system includes two phases with different thermal stabilities. Either of these two borides can be obtained by direct synthesis on adjusting the alkali-metal pressure in the vapor phase. Thus, the preparation of NaB can be carried out in isothermal reactors at < 1100°C (p a = 45 X 10 N m" ) where the equilibrium... 

Enhanced thermal stability enlarges the areas of application of protein films. In particular it might be possible to improve the yield of reactors in biotechnological processes based on enzymatic catalysis, by increasing the temperature of the reaction and using enzymes deposited by the LB technique. Nevertheless, a major technical difficulty is that enzyme films must be deposited on suitable supports, such as small spheres, in order to increase the number of enzyme molecules involved in the process, thus providing a better performance of the reactor. An increased surface-to-volume ratio in the case of spheres will increase the number of enzyme molecules in a fixed reactor volume. Moreover, since the major part of known enzymatic reactions is carried out in liquid phase, protein molecules must be attached chemically to the sphere surface in order to prevent their detachment during operation. 

This latter point was stressed by some of us in a recent report studying NO storage and reduction on commercial LSR (lean storage-reduction) catalysts, in order to catch valuable information about the behaviour of typical NO storage materials in real application conditions. Nature, thermal stability and relative amounts of the surface species formed on a commercial catalyst upon NO and 02 adsorption in the presence and in the absence of water were analysed using a novel system consisting of a quartz infrared reactor. Operando IR plus MS measurements showed that carbonates present in the fresh catalyst are removed by replacement with barium nitrate species after the first nitration of the material. Nitrate species coordinated to different barium sites are the predominant surface species under dry and wet conditions. The difference in the species stabilities suggested that barium sites possess different basicity and, therefore, that they are able to stabilize nitrates at different temperatures. At temperatures below 523 K, nitrite species were observed. The presence of water at mild temperatures in the reactant flow makes unavailable for NO adsorption the alumina sites [181]. 

It was found that the steam supply to the reactor was often superheated (just prior to shutdown to 330°C) [10], Although this degree of superheat would not grossly increase the temperature of the inner reactor wall in contact with the liquid (or the bulk liquid temperature) [11], it seems probable that any reaction material splashed onto and dried out at the top of the coil-heated wall would have become heated to a much higher temperature. Further detailed work on the thermal stability of the mixture showed that a previously unsuspected very slow exothermic decomposition existed, beginning at 180°C and proceeding at an appreciable rate only above 200°C, so that the exotherm was insufficient to heat the contents of the reactor from the last recorded temperature of 158°C to the decomposition temperature of 230°C in 7.5 h [12,13,14], It was concluded that an alternative (effectively an external) source of heat was necessary to account for the observed effect, and the residual superheat from the steam at 330°C seems to have been that source. 

All the above-mentioned methods will be discussed in this chapter. A number of filtration and reactor units that have been used in published work will be described and an overview of the different membrane materials will be given. As generally catalytic reactions deal with organic substrates and are usually carried out in an organic solvent, the membranes have to be solvent resistant. Thermal stability can also be an issue depending on the process conditions. 

The activity of Ti catalysts in SSP depends on the kind of stabilizer fed into the reactor. In the production of PET, phosphorous-containing chemicals are commonly added as stabilizers. These products improve the thermal stability, particularly in processing, which results in reduced degradation and discoloration and are therefore of importance with respect to quality. Such materials are added during the production of the prepolymer. These stabilizers are mainly based on phosphoric or phosphonic (phosphorous) acids or their esters. 

In 55% of the cases, the accidents could have been foreseen by use of risk analysis, and in 35% of the cases by thermal stability testing. Different methods of stability testing were evaluated comparatively during the investigation of a runaway exothermic reaction which occurred during the preparation of a component mixture for a sealing composition in a 1200 1 reactor only DSC was effective in identifying the cause of the hazard. 

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