Reactor mechanical limitations

A second source of difficulty is caused by the unavoidable empty space in recycle reactors. This limits their usefulness in some studies. Homogeneous reactions in the empty gas volume may interfere with heterogeneous catalytic measurements. Transient experiments could reveal much more information on various steps in the reaction mechanism but material in the empty space can obscure sharp changes. 

Mechanical limitations include the design temperature and pressure of the reactor and the regenerator. 

Reactor temperature is usually directly controlled by adjusting the slide valve openings or changing the pressure differential between the regenerator and reactor. Mechanical design conditions of the reactor systems can limit operating at more severe conditions. To debottleneck these limitations ... 

The current study was limited by viscosity due to mechanical limitation in reactor design. An experiment... 

GP 11[ [R 19[ Temperatures close to 1200 °C, near the mechanical limit of the ceramic reactor material, have been achieved [9, 115], With improved sealing and better material, processing could lead to 1300 °C [9],... 

These reactors employ small particles in the range 0.05 - 1.0 mm (0.0020 -0.039 in) with the minimum size being limited by filterability. Small diameters are used to provide as large an interface as possible, since the internal surface of porous pellets is poorly accessible to the liquid phase (Perry and Green, 1999). The catalyst concentration in slurry reactors is limited by the agitation power of the mechanical stirrer or by the gas flow. 

In normal conditions of operation, therefore, a nuclear power reactor system can respond to the requirements of the electrical power grid system, and the rate at which power can be increased will be dictated by the mechanical limits of the components, rather than by the reactor physics of the core. However, all reactors have systems by which shutdown rods can be—and in many cases are— automatically forced into the core to avoid circumstances that could endanger the plant ( Scram —said to have been formed from the term Safety Control Rod Axe Man at the first man-made reactor, Stagg Field, Chicago). 

Classification of fluidized-bed reactors Velocity limits of a bubbling bed Fluid mechanical models of the bubbling bed Complete modeling of the fluidized-bed reactor... 

Continuous-Flow Stirred-Tank Reactor. In a continuous-flow stirred-tank reactor (CSTR), reactants and products are continuously added and withdrawn. In practice, mechanical or hydrauHc agitation is required to achieve uniform composition and temperature, a choice strongly influenced by process considerations, ie, multiple specialty product requirements and mechanical seal pressure limitations. The CSTR is the idealized opposite of the weU-stirred batch and tubular plug-flow reactors. Analysis of selected combinations of these reactor types can be useful in quantitatively evaluating more complex gas-, Hquid-, and soHd-flow behaviors. 

Model Reactions. Independent measurements of interfacial areas are difficult to obtain in Hquid—gas, Hquid—Hquid, and Hquid—soHd—gas systems. Correlations developed from studies of nonreacting systems maybe satisfactory. Comparisons of reaction rates in reactors of known small interfacial areas, such as falling-film reactors, with the reaction rates in reactors of large but undefined areas can provide an effective measure of such surface areas. Another method is substitution of a model reaction whose kinetics are well estabUshed and where the physical and chemical properties of reactants are similar and limiting mechanisms are comparable. The main advantage of employing a model reaction is the use of easily processed reactants, less severe operating conditions, and simpler equipment. 

Direct Chlorination of Ethylene. Direct chlorination of ethylene is generally conducted in Hquid EDC in a bubble column reactor. Ethylene and chlorine dissolve in the Hquid phase and combine in a homogeneous catalytic reaction to form EDC. Under typical process conditions, the reaction rate is controlled by mass transfer, with absorption of ethylene as the limiting factor (77). Ferric chloride is a highly selective and efficient catalyst for this reaction, and is widely used commercially (78). Ferric chloride and sodium chloride [7647-14-5] mixtures have also been utilized for the catalyst (79), as have tetrachloroferrate compounds, eg, ammonium tetrachloroferrate [24411-12-9] NH FeCl (80). The reaction most likely proceeds through an electrophilic addition mechanism, in which the catalyst first polarizes chlorine, as shown in equation 5. The polarized chlorine molecule then acts as an electrophilic reagent to attack the double bond of ethylene, thereby faciHtating chlorine addition (eq. 6) ... 

The model that best describes the mechanism is usually very complicated. For dynamic studies that require much more computation (and on a more limited domain) a simplified model may give enough information as long as the formalities of the Arrhenius expression and power law kinetics are incorporated. To study the dynamic behavior of the ethylene oxide reactor. 

Remarks The aim here was not the description of the mechanism of the real methanol synthesis, where CO2 may have a significant role. Here we created the simplest mechanistic scheme requiring only that it should represent the known laws of thermodynamics, kinetics in general, and mathematics in exact form without approximations. This was done for the purpose of testing our own skills in kinetic modeling and reactor design on an exact mathematical description of a reaction rate that does not even invoke the rate-limiting step assumption. 

Similar approaches are applicable in the chemical industry. For example, maleic anhydride is manufactured by partial oxidation of benzene in a fixed catalyst bed tubular reactor. There is a potential for extremely high temperatures due to thermal runaway if feed ratios are not maintained within safe limits. Catalyst geometry, heat capacity, and partial catalyst deactivation have been used to create a self-regulatory mechanism to prevent excessive temperature (Raghaven, 1992). 

The properties of such materials are not measurably altered until subjected to doses in excess of a million rads. At these higher doses, the principal changes are due to chem decompn which, with very few exceptions, resnlt in a decrease in sensitivity to mechanical stimulus and also in a dimunition of expl output. The radiation doses normally encountered in neutron activation procedures range from a few rads for 14 MeV fast neutron activation to several thousand rads for thermal neutron activations in a nuclear reactor. Thus, such doses are well under the limit at which measurable changes can occur... 

Achieving steady-state operation in a continuous tank reactor system can be difficult. Particle nucleation phenomena and the decrease in termination rate caused by high viscosity within the particles (gel effect) can contribute to significant reactor instabilities. Variation in the level of inhibitors in the feed streams can also cause reactor control problems. Conversion oscillations have been observed with many different monomers. These oscillations often result from a limit cycle behavior of the particle nucleation mechanism. Such oscillations are difficult to tolerate in commercial systems. They can cause uneven heat loads and significant transients in free emulsifier concentration thus potentially causing flocculation and the formation of wall polymer. This problem may be one of the most difficult to handle in the development of commercial continuous processes. 

All these steps can influence the overall reaction rate. The reactor models of Chapter 9 are used to predict the bulk, gas-phase concentrations of reactants and products at point (r, z) in the reactor. They directly model only Steps 1 and 9, and the effects of Steps 2 through 8 are lumped into the pseudohomoge-neous rate expression, a, b,. ..), where a,b,. .. are the bulk, gas-phase concentrations. The overall reaction mechanism is complex, and the rate expression is necessarily empirical. Heterogeneous catalysis remains an experimental science. The techniques of this chapter are useful to interpret experimental results. Their predictive value is limited. 

The finishing reactors used for PET and other equilibrium-limited polymerizations pose a classic scaleup problem. Small amounts of the condensation product are removed using devolatilizers (rotating-disk reactors) that create surface area mechanically. They scale as... 

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