Endothermic reactor conditions

Figure 13.16 shows two possible thermal profiles for endothermic plug-fiow reactors. This time the temperature falls for low rates of heat addition and/or high heat of reaction. The temperature rises for the reverse conditions. Under conditions between the profiles shown in Fig. 13.16, a minimum can occur in the temperature profile at an intermediate point between the inlet and exit. 

Most chemical reactions are greatly affected by temperature. The previous chapters discussed reactions at isothermal condition, however, industrial reactors often operate under non-isothermal condition. This is because chemical reactions strongly depend on temperature, either absorbing (i.e., endothermic) or generating (i.e., exothermic) a large amount of heat. 

Hot spot formation witliin tlie reactor can result in catalyst breakdown or physical deterioration of tlie reactor vessel." If tlie endothermic cyanide reaction has ceased (e.g., because of poor catalyst performance), the reactor is likely to overheat. Iron is a decomposition catalyst for hydrogen cyanide and ammonia under the conditions present in the cyanide reactor, and e. posed iron surfaces in the reactor or reactor feed system can result in uncontrolled decomposition, which could in turn lead to an accidaital release by overheating and overpressure. 

The SCB distribution (SCBD) has been extensively studied by fractionation based on compositional difference as well as molecular size. The analysis by cross fractionation, which involves stepwise separation of the molecules on the basis of composition and molecular size, has provided information of inter- and intramolecular SCBD in much detail. The temperature-rising elution fractionation (TREE) method, which separates polymer molecules according to their composition, has been used for HP LDPE it has been found that SCB composition is more or less uniform [24,25]. It can be observed from the appearance of only one melt endotherm peak in the analysis by differential scanning calorimetry (DSC) (Fig. 1) [26]. Wild et al. [27] reported that HP LDPE prepared by tubular reactor exhibits broader SCBD than that prepared by an autoclave reactor. The SCBD can also be varied by changing the polymerization conditions. From the cross fractionation of commercial HP LDPE samples, it has been found that low-MW species generally have more SCBs [13,24]. 

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 ... 

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. 

Worz et al. stress a gain in reaction selectivity as one main chemical benefits of micro-reactor operation [110] (see also [5]). They define criteria that allow one to select particularly suitable reactions for this - fast, exothermic (endothermic), complex and especially multi-phase. They even state that by reaching regimes so far not accessible, maximum selectivity can be obtained [110], Although not explicitly said, maximum refers to the intrinsic possibilities provided by the elemental reactions of a process under conditions defined as ideal this means exhibiting isothermicity and high mass transport. 

In practice, of course, it is rare that the catalytic reactor employed for a particular process operates isothermally. More often than not, heat is generated by exothermic reactions (or absorbed by endothermic reactions) within the reactor. Consequently, it is necessary to consider what effect non-isothermal conditions have on catalytic selectivity. The influence which the simultaneous transfer of heat and mass has on the selectivity of catalytic reactions can be assessed from a mathematical model in which diffusion and chemical reactions of each component within the porous catalyst are represented by differential equations and in which heat released or absorbed by reaction is described by a heat balance equation. The boundary conditions ascribed to the problem depend on whether interparticle heat and mass transfer are considered important. To illustrate how the model is constructed, the case of two concurrent first-order reactions is considered. As pointed out in the last section, if conditions were isothermal, selectivity would not be affected by any change in diffusivity within the catalyst pellet. However, non-isothermal conditions do affect selectivity even when both competing reactions are of the same kinetic order. The conservation equations for each component are described by... 

If this trend is extrapolated to lower temperatures it is clear that at temperatures varying between -78 and -150°C for carbon—hydrogen bonds on various types of hydrocarbons, AF becomes zero and then endothermic. Under these conditions (AG < 0) the reaction with elemental fluorine will not and should not proceed at all Wfe have observed this in many cases experimentally. At temperatures as low as -150°C the reaction of fluorine with all studied organic compounds either does not occur or is extremely slow. We have occasionally reported reactions in the cryogenic reactor as low as -120°C. It should be explained that the — 120°C reported is the temperature of a single trap in a multizone reactor rather than that for the entire reactor. It is possible that fluorination occurs during the volatilization process at such low temperatures. 

The use of steam has a number of other advantages in the styrene process. The most important of these is that it acts as a source of internal heat supply so that the reactor can be operated adiabatic-ally. The dehydrogenation reaction is strongly endothermic, the heat of reaction at 560°C being (- AH) - 125,000 kJ/kmoL It is instructive to look closely at the conditions which were originally worked out for this process (Fig. 1.7). Most of the.steam, 90 per cent of the total used, is heated separately from the ethylbenzene stream, and to a higher temperature (7I0SC) than is required at the inlet to the... 

Equation (3.3) shows the individual heats that contribute to overall heat gain and loss. The reaction heat, A//rxn, is positive for endothermic reactions and negative for exothermic reactions. The heat loss to the environment is shown as A/7iOSs- The heat supplied to the reactor, usually in the form of electric heating, is AHe but other forms of heating, for example, radiative, can be used instead of the electric heater. The baseline condition applies when no chemical reaction takes place. 

Kolios et al. [106] performed an extensive study revealing that coupling of exothermic and endothermic reactions is possible under safe and stable operation conditions only in catalytic wall reactors and not in coupled packed beds. In the latter case instability and thermal runaway of the reactor may occur. Additionally, the two... 

The design of chemical reactors encompasses at least three fields of chemical engineering thermodynamics, kinetics, and heat transfer. For example, if a reaction is run in a typical batch reactor, a simple mixing vessel, what is the maximum conversion expected This is a thermodynamic question answered with knowledge of chemical equilibrium. Also, we might like to know how long the reaction should proceed to achieve a desired conversion. This is a kinetic question. We must know not only the stoichiometry of the reaction but also the rates of the forward and the reverse reactions. We might also wish to know how much heat must be transferred to or from the reactor to maintain isothermal conditions. This is a heat transfer problem in combination with a thermodynamic problem. We must know whether the reaction is endothermic or exothermic. 

Most reactors used in industrial operations run isother-mally. For adiabatic operation, principles of thermodynamics are combined with reactor design equations to predict conversion with changing temperature. Rates of reaction normally increase with temperature, but chemical equilibrium must be checked to determine ultimate levels of conversion. The search for an optimum isothermal temperature is common for series or parallel reactions, since the rate constants change differently for each reaction. Special operating conditions must be considered for any highly endothermic or exothermic reaction. 

---