Catalyst Shapes and Production of Heterogeneous Catalysts

Catalyst Shapes and Production of Heterogeneous Catalysts Exercise 6.3... 

Industrial catalysts are generally shaped bodies of various forms, e.g., rings, spheres, tablets, pellets (Fig. 6-1). Honeycomb catalysts, similar to those in automobile catalytic converters, are also used. The production of heterogeneous catalysts consists of numerous physical and chemical steps. The conditions in each step have a decisive influence on the catalyst properties. Catalysts must therefore be manufactured under precisely defined and carefully controlled conditions [14]. 

Sdectivity - a very important plus for many heterogeneous catalysts whereby the pore structure Hmits the diffusion in for reactants or out for products effectively restricting the chemistry that occurs and the shape and size of molecules that can react or be formed shape selectivity can also affect the stereochemistry through the control of reaction pathways (e.g., use of zeoHtes to hmit the alkylation of benzene to mono-substituted products). 

Before deriving the rate equations, we first need to think about the dimensions of the rates. As heterogeneous catalysis involves reactants and products in the three-dimensional space of gases or liquids, but with intermediates on a two-dimensional surface we cannot simply use concentrations as in the case of uncatalyzed reactions. Our choice throughout this book will be to express the macroscopic rate of a catalytic reaction in moles per unit of time. In addition, we will use the microscopic concept of turnover frequency, defined as the number of molecules converted per active site and per unit of time. The macroscopic rate can be seen as a characteristic activity per weight or per volume unit of catalyst in all its complexity with regard to shape, composition, etc., whereas the turnover frequency is a measure of the intrinsic activity of a catalytic site. 

In any catalyst selection procedure the first step will be the search for an active phase, be it a. solid or complexes in a. solution. For heterogeneous catalysis the. second step is also deeisive for the success of process development the choice of the optimal particle morphology. The choice of catalyst morphology (size, shape, porous texture, activity distribution, etc.) depends on intrinsic reaction kinetics as well as on diffusion rates of reactants and products. The catalyst cannot be cho.sen independently of the reactor type, because different reactor types place different demands on the catalyst. For instance, fixed-bed reactors require relatively large particles to minimize the pressure drop, while in fluidized-bed reactors relatively small particles must be used. However, an optimal choice is possible within the limits set by the reactor type. 

In the presence of catalysts, heterogeneous catalytic cracking occms on the surface interface of the melted polymer and solid catalysts. The main steps of reactions are as follows diffusion on the surface of catalyst, adsorption on the catalyst, chemical reaction, desorption from the catalyst, diffusion to the liquid phase. The reaction rate of catalytic reactions is always determined by the slowest elementary reaction. The dominant rate controller elementary reactions are the linking of the polymer to the active site of catalyst. But the selectivity of catalysts on raw materials and products might be important. The selectivity is affected by molecular size and shape of raw materials, intermediates and products [36]. 

Heterogeneous catalysts are defined as solids or mixture of solids that are used to accelerate a chemical reaction without undergoing change themselves. The types of solids used in industry as heterogeneous catalysts include simple oxides, mixed oxides, metal salts, solid acids and bases, metals, and dispersed metals. Catalysts are used in a wide variety of chemical and environmental processes worldwide. The global value of fuels and chemicals produced by catalytic routes is about US 2.4-3 trillion per year. About 20% of all products produced in the United States are derived from a catalytic process of some form. As important as catalysis is to the world economy, the number of various chemicals used as a catalyst as well as the form and shape of the material vary as much as the number of processes that use catalysts. Fig. 1 is a picture of a number of various types of catalysts and illustrates the numerous possibilities of shapes and sizes. Naturally, the preparation processes of such a wide variety of products is also numerous. 

Metallic oxides having different shapes and sizes have received considerable attention because of their theoretical, technological applications in various organic reactions. Catalysts, for example, are mostly nanoscale particles, and catalysis is a nanoscale phenomenon. In the case of various reactions, separation of the catalyst from the reaction mixture is the main problem and loss of product occurs. Nano-particles prepared on the resin can easily be applied as a heterogeneous catalyst for efficient recovery and recycling of the photocatalyst from liquid-phase reactions. 

One of the most active areas of research in dehydration reactions is the use of heterogeneous catalysts (such as metal oxides, alumina, and zeolites) to catalyze the elimination of water from alcohols. Not only do the catalysts lower the temperatures required for dehydration, but they can also alter product distributions. For example, dehydration of 2-butanol produced 45% of 1-butene when the dehydration was catalyzed by alumina but 90% of 1-butene when zirconia was the catalyst. A wide variety of mechanisms have been considered for these reactions. The effect of the catalyst is a function of the nature of the acidic and basic sites on the catalyst surface, the size of openings into which organic molecules may fit, molecular shape, and... 

It has been already emphasized that substitution of heteroelements into the framework of molecular sieves creates acidic sites. Incorporation of transition elements such as Ti, V, Mn, Fe, or Co, which have redox properties, provides molecular sieves with redox active sites that are involved in oxidation reactions (323-332). As mentioned in the beginning of the article, the transition metal-substituted molecular sieves, the so-called redox molecular sieves, exhibit several advantages compared with other types of heterogeneous redox catalysts (1) redox sites are isolated in a well-defined internal structure therefore, oligomerization of the active oxometal species is prevented (this is a major reason for the deactivation of homogeneous catalysts) (2) the site isolation (the so-called microenvironment) of redox centers prevents the leaching of the metal ions, which frequently happens in liquid-phase oxidations catalyzed by conventional transition metal-supported catalysts (3) well-defined cavities and channels of molecular dimensions endow the catalysts with unique performances such as the shape selectivity (and traffic control) toward reactants, intermediates, and/or products. 

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