Fluid—Solid Reaction Kinetics

To consider fluid—solid reaction kinetics a generalized reaction will be considered ... 

In a fixed-bed catalytic reactor for a fluid-solid reaction, the solid catalyst is present as a bed of relatively small individual particles, randomly oriented and fixed in position. The fluid moves by convective flow through the spaces between the particles. There may also be diffusive flow or transport within the particles, as described in Chapter 8. The relevant kinetics of such reactions are treated in Section 8.5. The fluid may be either a gas or liquid, but we concentrate primarily on catalyzed gas-phase reactions, more common in this situation. We also focus on steady-state operation, thus ignoring any implications of catalyst deactivation with time (Section 8.6). The importance of fixed-bed catalytic reactors can be appreciated from their use in the manufacture of such large-tonnage products as sulfuric acid, ammonia, and methanol (see Figures 1.4,11.5, and 11.6, respectively). 

The kinetics and rate-controlling steps of a fluid-solid reaction are deduced by noting how the progressive conversion of particles is influenced by particle size and operating temperature. This information can be obtained in various ways, depending on the facilities available and the materials at hand. The following observations are a guide to experimentation and to the interpretation of experimental data. 

Figure 3. Transition from the kinetic regime to the diffusion-controlled regime of a heterogeneous catalytic fluid-solid reaction carried out on a porous catalyst.

Fluid-solid reactions include thermal decomposition of minerals, roasting (oxidation) of sulfide ores, reduction of metal oxides with hydrogen, nitridation of metals, and carburization of metals. Each t3 e of reaction will be discussed finm the thermodynamic point of view. Then reaction kinetics for all of the various rate determining steps in fluid-sohd reactions will be discussed for two general models shrinking core and shrinking particle. 

A fluid for our consideration here is either a liquid or a gas. Fluid-solid reactions can be kinetically limited by several steps [8] ... 

Fluid-solid reactions can be kinetically limited by several steps ... 

Heterogeneous Reaction Systems The mathematical treatment is quite different if the exchanger is neated as a solid phase. The conceptual models are then similar to (hose developed for noucatalytic fluid-solid reactions.17 18 These kinetic models have been applied successfully to some ion-exchange processes. I9"51... 

Bhatia SK, Perlmntter DD (1980) A random pore model for fluid-solid reactions I. Isothermal, kinetic control. AIChE J 26 379-386... 

In this chapter, the various characteristics of MSR for fluid-solid reactions are presented. It is clear that microreactors are mostly suitable for reactions that have fast intrinsic kinetics and require rapid transport, are carried out at high temperatures and pressures, and, therefore, ensure inherent safety. Effective exploitation of the full chemical potential of catalysts through high rates of heat and mass transfer provides an excellent means for identifying novel synthesis routes that are both economically attractive and environmentally benign. 

ABSTRACT. Characteristics and fluid dynamics of gas phase recirculation in a novel Riser Simulator Reactor have been investigated using constant temperature hot wire anemometry. In situ concentration and velocity measurements enabled to evaluate the mixing time and the inner recirculation ratio of the gas phase. In addition, fibre optic techniques allowed to characterize the degree of fluidization of the catalyst particles and the effect of gas phase density changes. By combining the anemometry and the fibre optic techniques, mixing patterns in the Riser Simulator have been evaluated. The importance of the study can be realized in the context of the potential use of the Riser Simulator for gas-solid reaction kinetics. 

FIG. 16-9 General scheme of adsorbent particles in a packed bed showing the locations of mass transfer and dispersive mechanisms. Numerals correspond to mimhered paragraphs in the text 1, pore diffusion 2, solid diffusion 3, reaction kinetics at phase boundary 4, external mass transfer 5, fluid mixing. 

The reaction kinetics approximation is mechanistically correct for systems where the reaction step at pore surfaces or other fluid-solid interfaces is controlling. This may occur in the case of chemisorption on porous catalysts and in affinity adsorbents that involve veiy slow binding steps. In these cases, the mass-transfer parameter k is replaced by a second-order reaction rate constant k. The driving force is written for a constant separation fac tor isotherm (column 4 in Table 16-12). When diffusion steps control the process, it is still possible to describe the system hy its apparent second-order kinetic behavior, since it usually provides a good approximation to a more complex exact form for single transition systems (see Fixed Bed Transitions ). 

Permissible gas velocities are usually set by entrainment, and for a given throughput the vessel diameter is thus determined. The amount of catalyst or other bed particles is set by reaction kinetics and the bubble-solids contacting expected. Very often there is a scale-up debit involved in fluid bed reactors. As mentioned earlier, small reactors... 

The packed-bed reactors discussed in Chapters 9 and 10 are multiphase reactors, but the solid phase is stationary, and convective flow occurs only through the fluid phase. The reaction kinetics are pseudohomogeneous, and components balances are written only for the fluid phase. 

If the reactant solid is porous, the reactant fluid would diffuse into it while reacting with it on its path diffusion and chemical reaction would occur in parallel over a diffuse zone. The analysis of such a reaction system is normally more complex as compared to reaction systems involving nonporous solids. Here also it is important to assess the relative importance of chemical reaction kinetics and of mass and heat transport. 

The reaction kinetics approximation is mechanistically correct for systems where the reaction step at pore surfaces or other fluid-solid interfaces is controlling. This may occur in the case of chemisorption on porous catalysts and in affinity adsorbents that involve very slow binding steps. In these cases, the mass-transfer parameter k is replaced... 

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