Catalyst pellet forms

Metal deposition occurs with sharp gradients within a catalyst pellet, usually concentrated on the outside of catalyst pellets forming a U-shaped distribution. Sato et at [3] related this metal deposition with simultaneous diffusion and reaction, and suggested a value of 8 for the Thiele modulus in a slab geometry, Tamm [4] suggested that this distribution can be characterized by a theta factor defined in a ( Undricat geometry as... 

One way to estimate the influence of transport processes is to use directly experimental results observed under given experimental conditions. In general, the experimentalist has information concerning observed reaction rates, bulk reactant concentrations, and temperature, as well as the catalyst pellet form and dimensions. With these details at hand, the Weisz module can be estimated. For example, for spherical catalytic particles, see Equation 2.180. 

Rapid formation of whisker carbon may result in spalling of the catalyst pellets forming dust or complete breakdown of the pellet. However, in case of slow build-up of carbon, the catalyst pellet may stay intact - even with high amounts of carbon as illustrated in Figure 5.37. 

Figure 9 The schematic diagram of the mesoscaie modei for a single catalyst pellet formed with microporous zeolite particles and support regions (macro-Zmesopore region).

In principle, Chen, given the flux relations there is no difficulty in constructing differencial equations to describe the behavior of a catalyst pellet in steady or unsteady states. In practice, however, this simple procedure is obstructed by the implicit nature of the flux relations, since an explicit solution of usefully compact form is obtainable only for binary mixtures- In steady states this impasse is avoided by using certain, relations between Che flux vectors which are associated with the stoichiometry of Che chemical reaction or reactions taking place in the pellet, and the major part of Chapter 11 is concerned with the derivation, application and limitations of these stoichiometric relations. Fortunately they permit practicable solution procedures to be constructed regardless of the number of substances in the reaction mixture, provided there are only one or two stoichiomeCrically independent chemical reactions. 

Despite the very restricted circumstances In which these equations properly describe the dynamical behavior, they are the starting point for almost all the extensive literature on the stability of steady states in catalyst pellets. It is therefore Interesting to examine the case of a binary mixture at the opposite limit, where bulk diffusion controls, to see what form the dynamical equations should take in a coarsely porous pellet. 

Apart from this simple result, comparison of stability predictions for the two limiting situations can be made only by direct numerical computation, and for this purpose a specific algebraic form must be assumed for the reaction rate function, and a specific shape for che catalyst pellet. In particular, Lee and Luss considered a spherical pellet and a first order... 

The scheme of commercial methane synthesis includes a multistage reaction system and recycle of product gas. Adiabatic reactors connected with waste heat boilers are used to remove the heat in the form of high pressure steam. In designing the pilot plants, major emphasis was placed on the design of the catalytic reactor system. Thermodynamic parameters (composition of feed gas, temperature, temperature rise, pressure, etc.) as well as hydrodynamic parameters (bed depth, linear velocity, catalyst pellet size, etc.) are identical to those in a commercial methana-tion plant. This permits direct upscaling of test results to commercial size reactors because radial gradients are not present in an adiabatic shift reactor. 

Ross (R2) measured liquid-phase holdup and residence-time distribution by a tracer-pulse technique. Experiments were carried out for cocurrent flow in model columns of 2- and 4-in. diameter with air and water as fluid media, as well as in pilot-scale and industrial-scale reactors of 2-in. and 6.5-ft diameters used for the catalytic hydrogenation of petroleum fractions. The columns were packed with commercial cylindrical catalyst pellets of -in. diameter and length. The liquid holdup was from 40 to 50% of total bed volume for nominal liquid velocities from 8 to 200 ft/hr in the model reactors, from 26 to 32% of volume for nominal liquid velocities from 6 to 10.5 ft/hr in the pilot unit, and from 20 to 27 % for nominal liquid velocities from 27.9 to 68.6 ft/hr in the industrial unit. In that work, a few sets of results of residence-time distribution experiments are reported in graphical form, as tracer-response curves. 

While the discovery of the catalytic properties of zeolites was driven by the desire to improve industrial prcKessing, the development of emission control catalysts was necessitated by governmental fiat. The first requirement was for 90+% removal of CO and of hydrocarbons, a goal which could not be met by oxidation with base metal oxides. To achieve the required spedfications during automobile operations, it was necessary to develop supported platinum catalysts. Originally the support was alumina in pellet form. Later platinum on cordierite was used in honeycomb form, containing 200-400 square channels per square inch. 

Fixed Bed Reactors. In its most basic form, a fixed bed reactor consists of a cylindrical tube filled with catalyst pellets. Reactants flow through the catalyst bed and are converted into products. Fixed bed reactors are often referred to as packed bed reactors. They may be regarded as the workhorse of the chemical industry with respect to the number of reactors employed and the economic value of the materials produced. Ammonia synthesis, sulfuric acid production (by oxidation of S02 to S03), and nitric acid production (by ammonia oxidation) are only a few of the extremely high tonnage processes that make extensive use of various forms of packed bed reactors. 

The Effectiveness Factor Analysis in Terms of Effective Diffusivities First-Order Reactions on Spherical Pellets. Useful expressions for catalyst effectiveness factors may also be developed in terms of the concept of effective diffusivities. This approach permits one to write an expression for the mass transfer within the pellet in terms of a form of Fick s first law based on the superficial cross-sectional area of a porous medium. We thereby circumvent the necessity of developing a detailed mathematical model of the pore geometry and size distribution. This subsection is devoted to an analysis of simultaneous mass transfer and chemical reaction in porous catalyst pellets in terms of the effective diffusivity. In order to use the analysis with confidence, the effective diffusivity should be determined experimentally, since it is difficult to obtain accurate estimates of this parameter on an a priori basis. 

If we consider a reaction with intrinsic kinetics of simple nth order form that takes place within the pores of a catalyst pellet, the observed rate of reaction per unit mass of catalyst may be written as... 

This relation is plotted as curve Bin Figure 12.11. Smith (66) has shown that the same limiting forms for are observed using the concept of effective dififusivities and spherical catalyst pellets. Curve B indicates that, for fast reactions on catalyst surfaces where the poisoned sites are uniformly distributed over the pore surface, the apparent activity of the catalyst declines much less rapidly than for the case where catalyst effectiveness factors approach unity. Under these circumstances, the catalyst effectiveness factors are considerably less than unity, and the effects of the portion of the poison adsorbed near the closed end of the pore are not as apparent as in the earlier case for small hr. With poisoning, the Thiele modulus hp decreases, and the reaction merely penetrates deeper into the pore. 

Spectra of a spent bauxite-based desulfurization catalyst pellet ( 7 x 13 mm, examined in air) are shown in Fig. 9. The outside of the pellet was black and the single-beam spectrum S showed some of the continuum absorption found with chars. The compensated spectrum S/So, however, showed appreciable spectral structure. The broad band near 750 cm is probably due to the bauxite, and the absorptions near 3000, 1320 and 1000 cm-- - to a mixture of hydrocarbons and thio species formed during the reaction. The feature near 1640 cm l is probably caused by an olefinnic species. 

The desire to have catalysts that were uniform in composition and catalytic performance led to the development of synthetic catalysts. The first synthetic cracking catalyst, consisting of 87% silica (Si02) and 13% alumina (AI2O3), was used in pellet form and used in fixed-bed units in 1940. Catalysts of this composition were ground and sized for use in fluid catalytic cracking units. In 1944, catalysts in the form of beads about 2.5 to 5.0 mm in diameter were introduced and comprised about 90% silica and 10% alumina and were extremely durable. One version of these catalysts contained a minor amount of chromia (Cr203) to act as an oxidation promoter. 

Decomposition of hydrogen sulfide. M0S2 catalyst either in layer form (see inner layer in previous column) or in pellet form (see alternative systems 1 and 2, below)... 

The modulus defined by eqn. (10) then has the advantage that the asymptotes to t (0) are approximately coincident for a variety of particle shapes and reaction orders, with the specific exception of a zero-order reaction (n = 0), for which t = 1 when 0 < 1 and 77 = 1/0 when 0 > 1. The curve of 77 as a function of 0 is thus quite general for practical catalyst pellets. Figure 2 illustrates the form of For 0 > 3, it is found that 77 = 1/0 to an accuracy within 0.5%, while the approximation is within 3.5% for 0 > 2. The errors involved in using the generalised curve to estimate 77 are probably no greater than the errors perpetrated by estimating values of parameters in the Thiele modulus. 

Wakao and Smith [20] originally developed the random pore model to account for the behaviour of bidisperse systems which contain both micro- and macro-pores. Many industrial catalysts, for example, when prepared in pellet form, contain not only the smaller intraparticle pores, but also larger pores consisting of the voids between compressed particles. Transport within the pellet is assumed to occur through void regions... 

Small amounts of other compounds can be added to Ni-based catalysts to improve the functional characteristics of the final catalyst. Typically, they are calcium aluminate to enhance the mechanical resistance of the catalyst pellets, potassium oxide to improve the resistance to coke formation and silica to form a stable silicate with potassium oxide [34]. Promotion with rare earth oxides such as La2C>3 also results in enhanced resistance to coking. 

The FCC reactor is really two reactors with sohd catalyst pellets cycled between them. The vaporized gas oil is fed along with fresh catalyst to the first, called the reactor, and the spent catalyst is separated from the products in a cyclone and sent to the regenerator, where air (now sometimes O2) is added to oxidize the carbon. The flows of reactants, products, air, and catalyst are indicated in Figure 2-13. The reactor cracks the hydrocarbon and forms coke on the catalyst Then in the regenerator the coke is burned off and the catalyst is sent back into the reactor. 

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