Exotherm

Temperature control. Let us now consider temperature control of the reactor. In the first instance, adiabatic operation of the reactor should be considered, since this leads to the simplest and cheapest reactor design. If adiabatic operation produces an unacceptable rise in temperature for exothermic reactions or an unacceptable fall in temperature for endothermic reactions, this can be dealt with in a number of ways ... 

Generally speaking, temperature control in fixed beds is difficult because heat loads vary through the bed. Also, in exothermic reactors, the temperature in the catalyst can become locally excessive. Such hot spots can cause the onset of undesired reactions or catalyst degradation. In tubular devices such as shown in Fig. 2.6a and b, the smaller the diameter of tube, the better is the temperature control. Temperature-control problems also can be overcome by using a mixture of catalyst and inert solid to effectively dilute the catalyst. Varying this mixture allows the rate of reaction in different parts of the bed to be controlled more easily. 

In addition to the advantage of high heat transfer rates, fluidized beds are also useful in situations where catalyst particles need frequent regeneration. Under these circumstances, particles can be removed continuously from the bed, regenerated, and recycled back to the bed. In exothermic reactions, the recycling of catalyst can be... 

This is an exothermic, reversible, homogeneous reaction taking place in a single liquid phase. The liquid butadiene feed contains 0.5 percent normal butane as an impurity. The sulfur dioxide is essentially pure. The mole ratio of sulfur dioxide to butadiene must be kept above 1 to prevent unwanted polymerization reactions. A value of 1.2 is assumed. The temperature in the process must be kept above 65°C to prevent crystallization of the butadiene sulfone but below lOO C to prevent its decomposition. The product must contain less than 0.5 wt% butadiene and less thM 0.3 wt% sulfur dioxide. 

Reaction temperature. For endothermic reactions. Fig. 2.9c shows that the temperature should be set as high as possible consistent with materials-of-construction limitations, catalyst life, and safety. For exothermic reactions, the ideal temperature is continuously decreasing as conversion increases (see Fig. 2.9c). 

Adiabatic operation. If adiabatic operation leads to an acceptable temperature rise for exothermic reactors or an acceptable fall for endothermic reactors, then this is the option normally chosen. If this is the case, then the feed stream to the reactor requires heating and the efiluent stream requires cooling. The heat integration characteristics are thus a cold stream (the reactor feed) and a hot stream (the reactor efiluent). The heat of reaction appears as elevated temperature of the efiluent stream in the case of exothermic reaction or reduced temperature in the case of endothermic reaction. 

Cold shot or hot shot. Injection of cold fresh feed for exothermic reactions or preheated feed for endothermic reactions to inter-... 

Figure 13.1a shows two possible thermal profiles for exothermic plug-fiow reactors. If the rate of heat removal is low and/or the heat of reaction is high, then the temperature of the reacting stream will increase along the length of the reactor. If the rate of heat removal is high and/or the heat of reaction is low, then the temperature will fall. Under conditions between the two profiles shown in Fig. 13.1a, a maximum can occur in the temperature at an intermediate point between the reactor inlet and exit. 

The thermal profile through the reactor will in most circumstances be carefully optimized to maximize selectivity, extend catalyst life, etc. Because of this, direct heat integration with other process streams is almost never carried out. The heat transfer to or from the reactor is instead usually carried out by a heat transfer intermediate. For example, in exothermic reactions, cooling might occur by boiling water to raise steam, which, in turn, can be used to heat cold streams elsewhere in the process. 

If the reactor can be matched with other process streams (which is unlikely), then the reactor profile should be included in the heat integration problem. This would be a hot stream in the case of an exothermic reaction or a cold stream in the case of an endothermic reaction. 

ANstreams = enthalpy change between feed and product streams AI/react = reaction enthalpy (negative in the case of exothermic reactions)... 

Figure 13.3 shows a process represented simply as a heat sink and heat source divided hy the pinch. Figure 13.3a shows the process with an exothermic reactor integrated above the pinch. The minimum hot utility can be reduced by the heat released by reaction, Qreact-... 

By comparison, Fig. 13.36 shows an exothermic reactor integrated below the pinch. Although heat is being recovered, it is being recovered into part of the process which is a heat source. The hot utility requirement cannot be reduced because the process above the pinch needs at least Q//m-,n to satisfy its enthalpy imbalance. 

There is no obvious benefit from integrating an exothermic reactor below the pinch. The appropriate placement for exothermic reactors is above the pinch. ... 

The reaction is exothermic, and multitubular reactors are employed with indirect cooling of the reactor via a heat transfer medium. A number of heat transfer media have been proposed to carry out the reactor cooling, such as hot oil circuits, water, sulfur, mercury, etc. However, the favored heat transfer medium is usually a molten heat transfer salt which is a eutectic mixture of sodium-potassium nitrate-nitrite. 

The reactor is highly exothermic, and the data have been extracted as the molten salt being a hot stream. The basis of this is that it is assumed that the molten salt circuit is an essential feature of the reactor design. Thereafter, there is freedom within reason to choose how the molten salt is cooled. 

The appropriate placement of reactors, as far as heat integration is concerned, is that exothermic reactors should be integrated above the pinch and endothermic reactors below the pinch. Care should be taken when reactor feeds are preheated by heat of reaction within the reactor for exothermic reactions. This can constitute cross-pinch heat transfer. The feeds should be preheated to pinch temperature by heat recovery before being fed to the reactor. 

The main reactions involved are the exothermic producer gas reactions, which are basically... 

The cloud point, usually between 0 and -10°C, is determined visually (as in NF T 07-105). It is equal to the temperature at which paraffin crystals normally dissolved in the solution of all other components, begin to separate and affect the product clarity. The cloud point can be determined more accurately by differential calorimetry since crystal formation is an exothermic phenomenon, but as of 1993 the methods had not been standardized. 

The highly exothermic reaction is catalyzed by strong acids sulfuric, hydrofluoric. 

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