Pore size, influencing shape selectivity

The data of Table I suggest that addition of alumina binder can have a marked influence on selectivity with minimization of polymer (> C4) formation. Deactivation via coke formation depends on the exact pore size and shape of the zeolite. The time it takes for each catalyst type to reach steady state is quite variable, i.e., 4 h for PER and 10 h for ZSM-22. The PER/AI2O3 catalyst has the best yield of all materials we have studied.6f. 62... 

Conducting reactions in nanospace where the dimensions of the reaction vessel are comparable to those of the reactants provides a new tool that can be used to control the selectivity of chemical transformations.1 This dimensional aspect of nano-vessels has been referred to as shape selectivity.2 The effect of spatial confinement can potentially be exerted at all points on the reaction surface but its influence on three stationary points along the reaction coordinate (reactants, transition states, and products) deserve special attention.3,4 (1) Molecular sieving of the reactants, excluding substrates of the incorrect dimension from the reaction site can occur (reactant selectivity). (2) Enzyme-like size selection or shape stabilization of transition states can dramatically influence reaction pathways (transition state selectivity). (3) Finally, products can be selectively retained that are too large to be removed via the nano-vessel openings/pores (product selectivity). 

Shape selective reactions are typically carried out over zeolites, molecular sieves and other porous materials. There are three major classifications of shape selectivity including (1) reactant shape selectivity where reactants of sizes less than the pore size of the support are allowed to enter the pores to react over active sites, (2) product shape selectivity where products of sizes smaller than the pore dimensions can leave the catalyst and (3) transition state shape selectivity where sizes of pores can influence the types of transition states that may form. Other materials like porphyrins, vesicles, micelles, cryptands and cage complexes have been shown to control product selectivities by shape selective processes. 

Post-synthesis methods (pore-size engineering) allow an existing shape-selectivity effect to be intensified, and also a new one to be established. However, normally not only the pore size will be influenced by most of these methods, but also the catalytic activity. Vansant [104] gives a classification of post-synthesis modification methods which covers the entire range of zeolite applications (gas separation, gas purification, encapsulation of gases and catalysis). 

Rollmann and Walsh (266) have recently shown that for a wide variety of zeolites there is a good correlation between shape-selective behavior, as measured by the relative rates of conversion of n-hexane and 3-methyl-pentane, and the rate of coke formation (see Fig. 24). This correlation was considered to provide good evidence that intracrystalline coking is itself a shape-selective reaction. Thus, the rather constrained ZSM-5 pore structure exhibits high shape selectivity, probably via a restricted transition-state mechanism (242b), and therefore has a low rate of coke formation. Zeolite composition and crystal size, although influencing coke formation, were found to be of secondary importance. This type of information is clearly... 

Obviously the pore size determines which molecules can access the acidic sites inside the zeolite framework (molecular sieving effect) and is responsible for the shape selectivity observed with these materials (see later). The catalytic activity is also influenced by the acid strength of these sites which is determined by the Si/Al ratio (see above). The latter can be increased by post-synthesis removal of A1 atoms. Dealumination can be achieved by treatment with a... 

The study of the textural properties of catalyst supports is of primary importance in terms of understanding the catalytic phenomena involved in petrochemical and refining industry processes. In fact, characteristics, such as the specific surface area, pore size or total porous volume will be useful in various stages of a catalyst s existence its preparation (deposition of active phases), its use in catalysis and its regeneration. They directly influence the physicochemical properties of the solid as well as surface reactivity, shape selectivity and hydrodynamic properties. 

The pore size of the zeolite influences the product distribution via suppression of the formation of the bulkier products. The condensation of acetone over NaX and NaL type zeolites is an example of this shape selectivity. As outlined above acetone is converted to diacetonalcohol and mesityloxide which may further react to isophorone. The product ratio of mesityloxide to the bulkier isophorone was 0.75 for zeolite X and 1.87 for zeolite L [138,139]. 

These processes are covered in other chapters of this text and will not be described herein. Factors such as substrate size, size distribution, shape, porosity, friability, and solubility may influence the release properties of the coated dosage form. The goal in coating is to apply the film in such a way that its release is governed by the intrinsic properties of the film, and not imperfection (core penetration, surface pores and defects, fines imbedded in the film, non-uniformity of distribution, etc.). In addition to the properties of the substrate and the coating material, the type of process selected may have a significant impact on the behavior of the finished product. 

The pore shape influences the mass transfer rate and thus the efficiency of separation. The effective diameter of pores determines the range of separated molar masses. The pore size distribution and the pore volume are decisive for selectivity of separation (section 4.6.2.3). The pore sizes of commercially available gels cover the region necessary for separation of the wide spectrum of substances — from low molecular samples to very high polymers, colloidal particles and viruses. The mean values of pore diameters range from few nanometers to about 2.5 /xm. Gels with various pore sizes, but of the same type, can be combined within the same column. 

Conversion over Unmodified H-ZSM-5 and H-US-Y - The influence of the pore structure of the zeolites on the product distribution of m- and p-cymene isomers has been studied in the presence of an unmodified shape-selective medium pore-sized H-ZSM-5-(55) and the unmodified H-US-Y zeolite at temperatures between 200 and 300 °C. In contrast to the H-US-Y, the p-cymene formation in the presence of H-ZSM-5 is favoured due to the shape selectivity. ... 

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