Catalyst particles structure

Metal catalysts composed of more than two different metal elements are of interest from both technological and scientific viewpoints for improving the catalyst quality or properties (20). In fact, bimetallic (or multimetallic) catalysts have long been valuable for in-depth investigations of the relationship between catalytic activity and catalyst particle structure (21). Sinfelt et al. have made a series of studies on bimetallic nanoparticle catalysts supported on inorganic supports, for example,... 

STM and Infrared Spectroscopy in Studies of Fuel Cell Model Catalysts Particle Structure and Reactivity... 

Figure 2.33 Polymer/catalyst particle structure according to the MGM. The catalyst particle (left, also called the secondary particle or macroparticle) Is composed of an aggregation of primary particles (microparticles) arranged in concentric spherical layers. Polymer forms around the microparticles causing the macroparticle to expand.

It may be questioned how representative a pore really is for a catalyst particle. No doubt in the future, with growing attention for the more detailed characterization of catalyst particle structures, more elaborate representations of the particle will be used. Beeckman and Froment [1982] developed the theory for reaction and deactivation by coke formation in random networks of pores. The deactivation was considered to occur through site coverage and pore blockage. Diffusion limitations were also included, but only for deactivation by site coverage. 

Three common uses of RBS analysis exist quantitative depth profiling, areal concentration measurements (atoms/cm ), and crystal quality and impurity lattice site analysis. Its primary application is quantitative depth profiling of semiconductor thin films and multilayered structures. It is also used to measure contaminants and to study crystal structures, also primarily in semiconductor materials. Other applications include depth profilii of polymers, high-T superconductors, optical coatings, and catalyst particles. ... 

The internal structure of the catalyst particle is often of a complex labyrinth-like nature, with interconnected pores of a multiplicity of shapes and sizes, In some cases, the pore size may be less than the mean free path of the molecules, and both molecular and Knudsen diffusion may occur simultaneously. Furthermore, the average length of the diffusion path will be extended as a result of the tortuousity of the channels. In view of the difficulty of precisely defining the pore structure, the particle is assumed to be pseudo-homogeneous in composition, and the diffusion process is characterised by an effective diffusivity D, (equation 10.8). 

Catalytic reactors can roughly be classified as random and structured reactors. In random reactors, catalyst particles are located in a chaotic way in the reaction zone, no matter how carefully they are packed. It is not surprising that this results in a nonuniform fiow over the cross-section of the reaction zone, leading to a nonuniform access of reactants to the outer catalyst surface and, as a consequence, undesired concentration and temperature profiles. Not surprisingly, this leads, in general, to lower yield and selectivity. In structured reactors, the catalyst is of a well-defined spatial structure, which can be designed in more detail. The hydrodynamics can be simplified to essentially laminar, well-behaved uniform fiow, enabling full access of reactants to the catalytic surface at a low pressure drop. 

A wealth of structures exists and can be found in the literature [1-3]. Figure 9.1 shows examples of monoliths and arrayed catalysts. MonoHths (Figure 9.1a) consist of parallel channels, whereas arrayed catalysts are built from structural elements that are similar to monolithic structures but containing twisted (zig-zag or skewed) passages and/or interconnected passages (Figure 9.1b,c) or arrays of packets of conventional catalyst particles located in the reaction zone in a structured way, whereby the position of particles inside the packets is random (Figure 9.1d). The latter are mainly used for catalytic distillation and are not discussed further in this chapter. 

The most important undesired metallic impurities are nickel and vanadium, present in porphyrinic structures that originate from plants and are predominantly found in the heavy residues. In addition, iron may be present due to corrosion in storage tanks. These metals deposit on catalysts and give rise to enhanced carbon deposition (nickel in particular). Vanadium has a deleterious effect on the lattice structure of zeolites used in fluid catalytic cracking. A host of other elements may also be present. Hydrodemetallization is strictly speaking not a catalytic process, because the metallic elements remain in the form of sulfides on the catalyst. Decomposition of the porphyrinic structures is a relatively rapid reaction and as a result it occurs mainly in the front end of the catalyst bed, and at the outside of the catalyst particles. 

However, these techniques may not detect important phenomena taking place on the surface of or within the interior of individual Inm-to Ipm-diameter inorganic particles that are s3rnthesized specifically for their catalytic activity. AEM is an extremely useful technique for analysis of the individual heterogeneous catalyst particle and its relationship to various supporting materials. Structural and chemical analyses can be obtained from specimen regions nearly 1000 times smaller than those studied by conventional bulk analysis techniques. This high lateral spatial... 

The valence band structure of very small metal crystallites is expected to differ from that of an infinite crystal for a number of reasons (a) with a ratio of surface to bulk atoms approaching unity (ca. 2 nm diameter), the potential seen by the nearly free valence electrons will be very different from the periodic potential of an infinite crystal (b) surface states, if they exist, would be expected to dominate the electronic density of states (DOS) (c) the electronic DOS of very small metal crystallites on a support surface will be affected by the metal-support interactions. It is essential to determine at what crystallite size (or number of atoms per crystallite) the electronic density of sates begins to depart from that of the infinite crystal, as the material state of the catalyst particle can affect changes in the surface thermodynamics which may control the catalysis and electro-catalysis of heterogeneous reactions as well as the physical properties of the catalyst particle [26]. 

Two ways to reduce the diffusion length in TBRs are 1) use of smaller catalyst particles, or 2) use of an egg-shell catalyst. The first remedy, however, will increase pressure drop until it becomes unacceptable, and the second reduces the catalyst load in the reaction zone, making the loads of the TBR and the MR comparable. For instance, the volumetric catalyst load for a bed of 1 mm spherical particles with a 0.1 mm thick layer of active material is 0.27. The corresponding load for a monolithic catalyst made from a commercial cordierite structure (square cells, 400 cpsi, wall thickness 0.15 mm), also with a 0.1 mm thick layer of active material, is 0.25. 

Molecular diffusion and/or Knudsen flow of reactants from the exterior surface of the catalyst particle into the interior pore structure. 

Scanning electron microscopy and other experimental methods indicate that the void spaces in a typical catalyst particle are not uniform in size, shape, or length. Moreover, they are often highly interconnected. Because of the complexities of most common pore structures, detailed mathematical descriptions of the void structure are not available. Moreover, because of other uncertainties involved in the design of catalytic reactors, the use of elaborate quantitative models of catalyst pore structures is not warranted. What is required, however, is a model that allows one to take into account the rates of diffusion of reactant and product species through the void spaces. Many of the models in common use simulate the void regions as cylindrical pores for such models a knowledge of the distribution of pore radii and the volumes associated therewith is required. 

Quantitative analytical treatments of the effects of mass transfer and reaction within a porous structure were apparently first carried out by Thiele (20) in the United States, Dam-kohler (21) in Germany, and Zeldovitch (22) in Russia, all working independently and reporting their results between 1937 and 1939. Since these early publications, a number of different research groups have extended and further developed the analysis. Of particular note are the efforts of Wheeler (23-24), Weisz (25-28), Wicke (29-32), and Aris (33-36). In recent years, several individuals have also extended the treatment to include enzymes immobilized in porous media or within permselective membranes. The important consequence of these analyses is the development of a technique that can be used to analyze quantitatively the factors that determine the effectiveness with which the surface area of a porous catalyst is used. For this purpose we define an effectiveness factor rj for a catalyst particle as... 

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