Reactor temperature endothermic reactions

Fired furnaces, kilns, and driers are special types of chemical reactor in which a combustible fuel (gas, oil, coal, wood, etc.) is burned in the presence of air to provide heat at a high temperature level. Generating high-pressure steam in power plants, providing heat in process units (distillation columns, reactors with endothermic reactions, etc.), producing lime, and smelting ore are common examples. 

Many effective control schemes have been established over the years for individual chemical units (Shinskey, 1988), For example, a tubular reactor usually requires control of inlet temperature. High-temperature endothermic reactions typically have a control system to adjust the fuel flowrate to a furnace supplying energy to the reactor. Crystallizers require manipulation of refrigeration load to control temperatui e. Oxygen concentration in the stack gas from a furnace is controlled to prevent excess fuel usage. Liquid solvent feed flow to an absorber is controlled as some ratio to the gas feed. We deal with the control of various unit operations in Chaps. 4 through 7. 

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 ... 

This is an endothermic reaction accompanied by an increase in the number of moles. High conversion is favored by high temperature and low pressure. The reduction in pressure is achieved in practice by the use of superheated steam as a diluent and by operating the reactor below atmospheric pressure. The steam in this case fulfills a dual purpose by also providing heat for the reaction. 

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. 

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. 

In the Godrej-Lurgi process, olefins are produced by dehydration of fatty alcohols on alumina in a continuous vapor-phase process. The reaction is carried out in a specially designed isothermal multitube reactor at a temperature of approximately 300°C and a pressure of 5—10 kPa (0.05—0.10 atm). As the reaction is endothermic, temperature is maintained by circulating externally heated molten salt solution around the reactor tubes. The reaction is sensitive to temperature fluctuations and gradients, hence the need to maintain an isothermal reaction regime. 

Fired reactors contain tubes or coils in which an endothermic reaction within a stream of reac tants occurs. Examples include steam/ hydrocarbon reformers, catalvst-filled tubes in a combustion chamber pyrolyzers, coils in which alkanes (from ethane to gas oil) are cracked to olefins in both types of reac tor the temperature is maintained up to 1172 K (1650°F). 

In general, for basic petrochemicals that are not much more expensive than fuel (energy) itself, the energy recovery or use is important. Therefore, exothermic reactions should be executed at the highest temperature and endothermic reaction at the lowest, within the range that the reaction permits. In addition, reactors should not be optimized only for their own performance, but also for the optimum economy of the full synthesis loop or the full technology. 

In the Monsanto/Lummus Crest process (Figure 10-3), fresh ethylbenzene with recycled unconverted ethylbenzene are mixed with superheated steam. The steam acts as a heating medium and as a diluent. The endothermic reaction is carried out in multiple radial bed reactors filled with proprietary catalysts. Radial beds minimize pressure drops across the reactor. A simulation and optimization of styrene plant based on the Lummus Monsanto process has been done by Sundaram et al. Yields could be predicted, and with the help of an optimizer, the best operating conditions can be found. Figure 10-4 shows the effect of steam-to-EB ratio, temperature, and pressure on the equilibrium conversion of ethylbenzene. Alternative routes for producing styrene have been sought. One approach is to dimerize butadiene to 4-vinyl-1-cyclohexene, followed by catalytic dehydrogenation to styrene ... 

As expected, heat exchanged per unit of volume in the Shimtec reactor is better than the one in batch reactors (15-200 times higher) and operation periods are much smaller than in a semibatch reactor. These characteristics allow the implementation of exo- or endothermic reactions at extreme operating temperatures or concentrations while reducing needs in purifying and separating processes and thus in raw materials. Indeed, since supply or removal of heat is enhanced, semibatch mode or dilutions become useless and therefore, there is an increase in selectivity and yield. 

In order to exemplify the potential of micro-channel reactors for thermal control, consider the oxidation of citraconic anhydride, which, for a specific catalyst material, has a pseudo-homogeneous reaction rate of 1.62 s at a temperature of 300 °C, corresponding to a reaction time-scale of 0.61 s. In a micro channel of 300 pm diameter filled with a mixture composed of N2/02/anhydride (79.9 20 0.1), the characteristic time-scale for heat exchange is 1.4 lO" s. In spite of an adiabatic temperature rise of 60 K related to such a reaction, the temperature increases by less than 0.5 K in the micro channel. Examples such as this show that micro reactors allow one to define temperature conditions very precisely due to fast removal and, in the case of endothermic reactions, addition of heat. On the one hand, this results in an increase in process safety, as discussed above. On the other hand, it allows a better definition of reaction conditions than with macroscopic equipment, thus allowing for a higher selectivity in chemical processes. 

Figure 6.4a shows the behavior of an endothermic reaction as a plot of equilibrium conversion against temperature. The plot can be obtained from values of AG° over a range of temperatures and the equilibrium conversion calculated as illustrated in Examples 6.1 and 6.2. If it is assumed that the reactor is operated adiabatically, a heat balance can be carried out to show the change in temperature with reaction conversion. If the mean molar heat capacity of the reactants and products are assumed constant, then for a given starting temperature for the reaction Ttn, the temperature of the reaction mixture will be proportional to the reactor conversion X for adiabatic operation, Figure 6.4a. As the conversion increases, the temperature decreases because of the reaction endotherm. If the reaction could proceed as far as equilibrium, then it would reach the equilibrium temperature TE. Figure 6.4b shows how equilibrium conversion can be increased by dividing the reaction into stages and reheating the reactants...

Reactor heat carrier. As pointed out in Chapter 7, if adiabatic operation is not possible and it is not possible to control temperature by indirect heat transfer, then an inert material can be introduced to the reactor to increase its heat capacity flowrate (i.e. product of mass flowrate and specific heat capacity). This will reduce temperature rise for exothermic reactions or reduce temperature decrease for endothermic reactions. The introduction of an extraneous component as a heat carrier effects the recycle structure of the flowsheet. Figure 13.6a shows an example of the recycle structure for just such a process. 

Cold shot. Injection of cold fresh feed for exothermic reactions or preheated feed for endothermic reactions to intermediate points in the reactor can be used to control the temperature in the reactor. Again, the heat integration characteristics are similar to adiabatic operation. The feed is a cold stream if it needs to be increased in temperature or vaporized and the product a hot stream if it needs to be decreased in temperature or condensed. If heat is provided to the cold shot or hot shot streams, these are additional cold streams. 

Reactor temperature. For endothermic reactions, Figure 6.8c 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, Figure 6.8c. 

This problem indicates the considerations that enter into the design of a tubular reactor for an endothermic reaction. The necessity of supplying thermal energy to the reactor contents at an elevated temperature implies that the heat transfer considerations will be particularly important in determining the longitudinal temperature profile of the reacting fluid. This problem is based on an article by Fair and Rase (1). 

Heat flow from any external thermo-source into the dehydrogenation reactor should take the role of affording the endothermic reaction heat and the evaporation heat of both reactant and product in addition to the apparent heat for raising their temperatures from the ambient up to the external heating one. Under assumptions of the sufficient amounts of active catalyst and the adequate feed rates of organic chemical hydride, the minimum required heat is obtained as shown in the example of methylcyclohexane at 285°C on the basis of 100% conversion of methylcyclohexane to toluene and hydrogen (Table 13.5). 

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