Reactor diffusion studies

The search for Turing patterns led to the introduction of several new types of chemical reactor for studying reaction-diffusion events in feedback systems. Coupled with huge advances in imaging and data analysis capabilities, it is now possible to make detailed quantitative measurements on complex spatiotemporal behaviour. A few of the reactor configurations of interest will be mentioned here. 

If a fluid is placed between two concentric cylinders, and the inner cylinder rotated, a complex fluid dynamical motion known as Taylor-Couette flow is established. Mass transport is then by exchange between eddy vortices which can, under some conditions, be imagmed as a substantially enlranced diflfiisivity (typically with effective diflfiision coefficients several orders of magnitude above molecular difhision coefficients) that can be altered by varying the rotation rate, and with all species having the same diffusivity. Studies of the BZ and CIMA/CDIMA systems in such a Couette reactor [45] have revealed bifiircation tlirough a complex sequence of front patterns, see figure A3.14.16. 

Gas-phase MR will undoubtedly find more widespread use in studies of catalysts and catalytic reactors initial studies have been done with thermally polarized gases. Clearly, it will be of interest to image gas flows in reactors in this application, the measurement strategies used to image gas and liquid flows will be similar. However, gas- and liquid-phase species diffusing within a porous catalyst will be influenced to differing extents by the physical and chemical characteristics of the catalyst. These... 

Numerous modeling studies of CVD reactors have been made and are summarized in recent review papers (I, 212). Table 3 in reference 212 lists major examples of CVD models up to mid-1986. Therefore, rather than giving an exhaustive list of previous work, Table V presents a summary of the major modeling approaches and forms the basis for the ensuing discussion, which is most appropriately handled in terms of two groups (1) hot-wall LPCVD systems and (2) cold-wall, near-atmospheric-pressure reactors. In LPCVD reactors, diffusion and surface reaction effects dominate, whereas in cold-wall reactors operated at near-atmospheric pressures, fluid flow and gas-phase reactions are important in predicting performance, as discussed earlier in relation to transport phenomena. 

Both types of diffusion studies require numerous difficult experiments in conventional reactors, and as a result they are rarely carried out. However, lacking the assurance that the kinetic data is free of extraneous effects, we cannot be sure that it can be reproduced in any other reactor. 

Figure 1. Flow diagram of reactor system for diffusion studies...

A series of experiments varying temperature, micro-sphere size and time on stream have been performed in a fixed fluidised bed microactivity reactor to study the role of intraparticle diffusion in commercial fluid catalytic cracking (FCC) catalysts, particularly on gasoline yield and catalyst deactivation by coke deposition, for the cracking of a vacuum gas oil. Additionally, a mechanistic model that describes interface and intrapartide mass transfer interactions with the cracking reactions, has been used to study the combined influence of pore size and intraparticle mass diffusion on the deactivation of FCC catalysts and the gasoline yield. 

In the worker health study commissioned by the Semiconductor Industry Association (SIA), the University of California study team looked at physical agents such as radioff equency (RF) radiation, and extremely low fi equency magnetic fields (ELF-MF) which arise from the use of electrical current, fifi They defined various ELF exposure parameters based on both fab and non-fab devices or equipment that might have a relevant ELF-MF. In the fab category they included ion implanters, sputterers, epitaxial reactors, diffusion furnaces, other furnaces, microscopes, fluorescent microscopes, and etchers/ashers. In the non-fab devices category they included microscopes, fluorescent microscopes, final test and probers. Figure 3 provides a box plot of the area levels for ELF-MF that were measured by the researchers during site visits. 

Along with optical methods, mass spectrometric methods are successfully used for analysis of stable and short-lived products in studying elementary reactions. These methods are combined with a jet reactor for studying reactions involving radicals. The diffusional variant of a jet reactor developed by A.M. Dodonov and V.A. Talroze is most successful. This method allows the detection of both radicals and excited species. The simplified scheme of the method is shown in Fig. 3.6. A sample is taken from a definite point along the axis of the diffusion cloud the removal of a capillary filled with the second reactant allows one to change the reaction time. To... 

At present, computational fluid dynamics methods are finding many new and diverse applications in bioengineering and biomimetics. For example, CFD techniques can be used to predict (1) velocity and stress distribution maps in complex reactor performance studies as well as in vascular and bronchial models (2) strength of adhesion and dynamics of detachment for mammalian cells (3) transport properties for nonhomogeneous materials and nonideal interfaces (4) multicomponent diffusion rates using the Maxwell-Stefan transport model, as opposed to the limited traditional Fickian approach. 

Example 17.1-2 The reaction rate in a large catalyst pellet We want to set up a packed-bed laboratory reactor to study a first-order reaction for which the rate constant is 18.6 sec We plan to use 0.6 cm spheres of a porous catalyst for this gas-phase reaction. The diffusion coefficient of reagents in these particles is about 0.027 cm /sec. 

Validation and Application. VaUdated CFD examples are emerging (30) as are examples of limitations and misappHcations (31). ReaUsm depends on the adequacy of the physical and chemical representations, the scale of resolution for the appHcation, numerical accuracy of the solution algorithms, and skills appHed in execution. Data are available on performance characteristics of industrial furnaces and gas turbines systems operating with turbulent diffusion flames have been studied for simple two-dimensional geometries and selected conditions (32). Turbulent diffusion flames are produced when fuel and air are injected separately into the reactor. Second-order and infinitely fast reactions coupled with mixing have been analyzed with the k—Z model to describe the macromixing process. 

Work in the area of simultaneous heat and mass transfer has centered on the solution of equations such as 1—18 for cases where the stmcture and properties of a soHd phase must also be considered, as in drying (qv) or adsorption (qv), or where a chemical reaction takes place. Drying simulation (45—47) and drying of foods (48,49) have been particularly active subjects. In the adsorption area the separation of multicomponent fluid mixtures is influenced by comparative rates of diffusion and by interface temperatures (50,51). In the area of reactor studies there has been much interest in monolithic and honeycomb catalytic reactions (52,53) (see Exhaust control, industrial). Eor these kinds of appHcations psychrometric charts for systems other than air—water would be useful. The constmction of such has been considered (54). 

For many laboratoiy studies, a suitable reactor is a cell with independent agitation of each phase and an undisturbed interface of known area, like the item shown in Fig. 23-29d, Whether a rate process is controlled by a mass-transfer rate or a chemical reaction rate sometimes can be identified by simple parameters. When agitation is sufficient to produce a homogeneous dispersion and the rate varies with further increases of agitation, mass-transfer rates are likely to be significant. The effect of change in temperature is a major criterion-, a rise of 10°C (18°F) normally raises the rate of a chemical reaction by a factor of 2 to 3, but the mass-transfer rate by much less. There may be instances, however, where the combined effect on chemical equilibrium, diffusivity, viscosity, and surface tension also may give a comparable enhancement. 

Pore diffusion limitation was studied on a very porous catalyst at the operating conditions of a commercial reactor. The aim of the experiments was to measure the effective diffiisivity in the porous catalyst and the mass transfer coefficient at operating conditions. Few experimental results were published before 1970, but some important mathematical analyses had already been presented. Publications of Clements and Schnelle (1963) and Turner (1967) gave some advice. 

Table 4-4 summarizes the ratings of the various reactors. The CFSTR and the recirculating transport reactor are the best choices because they are satisfactory in every category except for construction. The stirred batch and contained solid reactors are satisfactory if the catalyst under study does not decay. If the system is not limited by internal diffusion in the catalyst pellet, larger pellets could be used and the stirred-contained solids reactor is the better choice. However,... 

Glaser and Litt (G4) have proposed, in an extension of the above study, a model for gas-liquid flow through a b d of porous particles. The bed is assumed to consist of two basic structures which influence the fluid flow patterns (1) Void channels external to the packing, with which are associated dead-ended pockets that can hold stagnant pools of liquid and (2) pore channels and pockets, i.e., continuous and dead-ended pockets in the interior of the particles. On this basis, a theoretical model of liquid-phase dispersion in mixed-phase flow is developed. The model uses three bed parameters for the description of axial dispersion (1) Dispersion due to the mixing of streams from various channels of different residence times (2) dispersion from axial diffusion in the void channels and (3) dispersion from diffusion into the pores. The model is not applicable to turbulent flow nor to such low flow rates that molecular diffusion is comparable to Taylor diffusion. The latter region is unlikely to be of practical interest. The model predicts that the reciprocal Peclet number should be directly proportional to nominal liquid velocity, a prediction that has been confirmed by a few determinations of residence-time distribution for a wax desulfurization pilot reactor of 1-in. diameter packed with 10-14 mesh particles. 

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