Adiabatic reaction control

Since the incoming reaction gases in most cases must be heated to the ignition temperature of the catalytic reaction, adiabatic reaction control is often coupled with heat exchange between the incoming and exiting reaction gas resulting in so-called autothermal reaction control. This type of reaction control offers certain specific features and development perspectives, which are discussed in Section 10.1.3.4. 

Continuous ideal tubular reactor with adiabatic reaction control... 

The most widely used types of reactor for heterogeneously catalyzed reactions in the chemical and petrochemical industries are fixed-bed and fluidized-bed reactors [T26]. The most important reactors for heterogeneously catalyzed reactions are the fixed-bed reactors. They can be classified according to the manner in which the temperature is controlled into reactors with adiabatic reaction control, reactors with autothermal reaction control, and those with reaction control by removal or supply of heat in the reactor. Some of the well-known reactor designs are discussed below. 

Because this reaction is highly exothermic, the equiUbrium flame temperature for the adiabatic reaction with stoichiometric proportions of hydrogen and chlorine can reach temperatures up to 2490°C where the equiUbrium mixture contains 4.2% free chlorine by volume. This free hydrogen and chlorine is completely converted by rapidly cooling the reaction mixture to 200°C. Thus, by properly controlling the feed gas mixture, a burner gas containing over 99% HCl can be produced. The gas formed in the combustion chamber then flows through an absorber/cooler to produce 30—32% acid. The HCl produced by this process is known as burner acid. 

Example 14.6 derives a rather remarkable result. Here is a way of gradually shutting down a CSTR while keeping a constant outlet composition. The derivation applies to an arbitrary SI a and can be extended to include multiple reactions and adiabatic reactions. It is been experimentally verified for a polymerization. It can be generalized to shut down a train of CSTRs in series. The reason it works is that the material in the tank always experiences the same mean residence time and residence time distribution as existed during the original steady state. Hence, it is called constant RTD control. It will cease to work in a real vessel when the liquid level drops below the agitator. 

Strong interactions are observed between the reacting solute and the medium in charge transfer reactions in polar solvents in such a case, the solvent effects cannot be reduced to a simple modification of the adiabatic potential controlling the reactions, since the solvent nuclear motions may become decisive in the vicinity of the saddle point of the free energy surface (FES) controlling the reaction. Also, an explicit treatment of the medium coordinates may be required to evaluate the rate constant preexponential factor. 

In the second configuration (hybrid combustor), only a portion of the fuel is fed to the catalyst section. The inlet air/fuel ratio is carefully controlled to limit the adiabatic reaction temperature typically below 1000 °C, and accordingly, to reduce the catalyst thermal stresses. The remaining amount of fuel is fed to a... 

The enrichment of the concentration of the polar solvent component in the cage and, therefore, the relative amount of the red shift of the fluorescence band is a function of viscosity, since the diffusion-controlled reaction time must be smaller than the excited-state lifetime. This lifetime limitation of the red shift is even more severe if the higher value of the excited-state dipole moment is not a property of the initial Franck-Condon state but of the final state of an adiabatic reaction. Nevertheless, the additional red shift has been observed for the fluorescence of TICT biradical excited states due to their nanosecond lifetime together with a quenching effect of the total fluorescence since the A to 50 transition is weak (symmetry forbidden) (Fig. 2.25). 

The trajectory is a useful tool in the study of strategies of temperature control. For an adiabatic reaction the trajectory is linear and any cooling results in a deviation from this linear trajectory. This tool is demonstrated in the next section. 

Thus, the lower starting temperature controls the reaction temperature in a smooth way. The polytropic reaction control is often used to this purpose. In addition, it detects the initiation of the reaction, proved by the temperature increase during the adiabatic phase. 

The temperature control of the CSTR can be realized in different ways, such as an adiabatic reaction without cooling system or with jacket cooling. These different modes of operation, and the effect of the operating parameters on the stability of the reactor, are described in the following subsections. 

Panke et al. (2003) also demonstrated enhanced reaction control, with respect to the temperature-sensitive synthesis of 2-methyl-4-nitro-5-propyl-2H-pyrazole-3-carboxylic acid 219, a key intermediate in the synthesis of the lifestyle drug Sildenafil (220) (Scheme 64). When performing the nitration of 2-methyl-5-propyl-2H-pyrazole-3-carboxylic acid 219 under adiabatic conditions, with a dilution of 6.01kg 1), Dale et al. (2000) observed a temperature rise of 42 °C (from 50 to 92 °C) upon addition of the nitrating solution. As Scheme 63 illustrates, this proved problematic as at 100 °C decomposition of the product 219 was observed and in order to reduce thermal decomposition of pyrazole 219, and increase process safety, the authors investigated addition of the nitrating solution in three aliquots, which resulted in a reduced reaction temperature of 71 °C and an increase in chemoselectivity unfortunately, the reaction time was increased from 8 to 10 h. 

Given that external mass transfer is the controlling step in a catalyzed exothermic reaction, derive the equation for the surface temperature and relate the temperature difference to the adiabatic temperature rise. Show that under some conditions the surface temperature could exceed the adiabatic reaction temperature. 

Very frequently non-optimal setpoint trajectories are used for controlling reactor temperatures in batch reactors [25,39,179,180]. Reactor temperatures maybe allowed to increase from ambient temperatures up to a maximum temperature value, in order to use the heat released by reaction to heat the reaction medium and save energy (reduce energy costs). The temperature increase is almost always performed linearly, because of hardware limitations and simplicity of controller programming. After reaching the maximum allowed temperature value, reactor temperature is kept constant for a certain time interval, for production of polymer material at isothermal conditions. At the end of the batch, the reaction temperature is increased in order to reduce the residual monomer content of the final resin, usually with the help of a second catalyst. Heuristic optimum temperature trajectories were also formulated for batch polymerizations of acrylamide and quaternary ammonium cationic monomers, in order to use the available heat of reaction [181]. The batch time was split into two batch periods an isothermal reaction period and an adiabatic reaction period. 

For gases, where Le = 1, Eqn. (9-48) shows that Ihe surface of Ihe catalyst can be very hot (or cold) when the reaction is controlled by external mass transfer. In fact, flie temperature at the surface of the catalyst particle can approach the adiabatic reaction temperature, 7b + A7ad-This is especially troublesome for exothermic reactions where A7ad is large. 

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 ... 

The reaction occurs at essentially adiabatic conditions with a large temperature rise at the inlet surface of the catalyst. The predominant temperature control is thermal ballast in the form of excess methanol or steam, or both, which is in the feed. If a plant is to produce a product containing 50 to 55% formaldehyde and no more than 1.5% methanol, the amount of steam that can be added is limited, and both excess methanol and steam are needed as ballast. Recycled methanol requited for a 50—55% product is 0.25—0.50 parts per part of fresh methanol (76,77). 

In the CDTECH process (formerly CR L technology), the first reactor is adiabatic. The heat of reaction is removed pardy by vaporization of the reaction mix. The operating temperature is controlled by adjusting the operating pressure. 

Chlorine free radicals used for the substitutioa reactioa are obtaiaed by either thermal, photochemical, or chemical means. The thermal method requites temperatures of at least 250°C to iaitiate decomposition of the diatomic chlorine molecules iato chlorine radicals. The large reaction exotherm demands close temperature control by cooling or dilution, although adiabatic reactors with an appropriate diluent are commonly used ia iadustrial processes. Thermal chlorination is iaexpeasive and less sensitive to inhibition than the photochemical process. Mercury arc lamps are the usual source of ultraviolet light for photochemical processes furnishing wavelengths from 300—500 nm. 

Adiabatic. Control gas flow and/or solids feed rate so that the heat of reaction is removed as sensible heat in off gases and solids or heat supphed by gases or solids. 

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