Catalysis by solids

Catalysis by solids depends on the amount of surface exposed to the fluid. Large specific surface is obtained with small particles, but primarily with highly porous structures. For instance, to achieve 1 m2/cc the diameter of a sphere must be reduced to 6(10-4) cm, but porous catalysts may have several hundred m2/cc. Practical limitations exist to the smallness of particles that can be used, such as pressure drop and entrainment. In fixed or moving beds, particle diameters are several millimeters, in fluidized beds they may be less than 0.1 mm. 

Catalysis by Solid Acids. Two aspects are considered here. The first aspect is concerned with transesterification reactions catalyzed by solid acids. Unfortunately, little research dealing with this subject has been reported in the literature. The second aspect deals with esterification reactions of carboxylic acids (or FFAs). This second part addresses an important characteristic of inexpensive TG feedstocks, i.e., high FFA content. Ideally, an active solid catalyst should be able to carry out transesterification and esterification simultaneously, thus eliminating pretreatment steps. It is likely that heterogeneous catalysts that perform well in esterification should also be good candidates for transesterification since the mechanisms for both reactions are quite similar. 

The prospects of obtaining a detailed molecular-level understanding of heterogeneous catalysts would appear to be best for solid acids (1). Catalysis by solid acids often involves an appreciable concentration of reasonably uniform sites and restricted roles for defect structures. Furthermore, the great number of reaction studies, physical property measurements, and spectroscopic studies of solid acids provides a background (2-4) for the design and evaluation of further experimental and theoretical work. 

In the first chapter, Bates and van Santen summarize the theoretical foundations of catalysis in acidic zeolites. Being the most important crystalline materials used as catalysts, zeolites have been the obvious starting point for applications of theory to catalysis by solids and surfaces. Impressive progress has been made in the application of theory to account for transport, sorption, and reaction in zeolites, and the comparisons with experimental results indicate some marked successes as well as opportunities for improving both the theoretical and experimental foundations. 

The interest and activity in metal complex catalysis will continue to be marked by further advances in asymmetric catalysis and catalysis by solid metal complexes as well as in the discovery of new complexes capable of catalytically activating molecules such as hydrocarbons, nitrogen, oxygen, and carbon dioxide in a manner that permits new uses for these abundant materials. 

Olah, G.A., Yamato, T., Iyer, P.S. and Prakash, G.K.S., Catalysis by solid superacids. 20. Nafion-H catalyzed reductive cleavage of acetals and ketals to ethers with triethylsilane, /. Org. Chem., 1986, 51, 2826. 

As will be described in more detail in later sections, in acid and oxidation catalysis by solid heteropoly compounds, that is, gas-solid and liquid-solid systems, there are three different classes of catalysis (1) surface catalysis, (2) bulk type 1 (pseudoliquid catalysis), and (3) bulk type II catalysis, as shown in Fig. 1. The latter two have been specifically demonstrated for heteropoly catalysts, and they could be found for other solid catalysts as well. 

Heteropolyanions and isopolyanions are polymeric oxoanions (polyoxometalates) (2, 3, 5, 6). The structure of a heteropolyanion or polyoxoanion molecule itself is called a primary structure (5, 6, 77). There are various kinds of polyoxoanion structure (Section II.A. 1). In solution, heteropoly anions are present in the unit of the primary structure, being coordinated with solvent molecules and/ or protonated. Most heteropolyanions tend to hydrolyze readily at high pH (Section 1I.C). Protonation and hydrolysis of the primary structure may be major structural concerns in solution catalysis. Heteropoly compounds in the solid state are ionic crystals (sometimes amorphous) consisting of large polyanions, cations, water of crystallization, and other molecules. This three-dimensional arrangement is called the secondary structure. For understanding catalysis by solid heteropoly compounds, it is important to distinguish between the primary structure and the secondary structure (5, 6, 17). Recently, it has been realized that, in addition... 

To understand oxidation catalysis by solid heteropoly compounds, the contrast between surface and bulk type II catalysis, and acid-redox bifunctionality... 

Tanabe, K. Catalysis by solid bases and related subjects. In Catalysis by Acids and Bases, B. Imelik et al. (eds). Elsevier, Amsterdam, 1985. 

The replacement of homogeneous catalysis by solid catalysts brings obvious economical and technological advantages. For this reason, a considerable research effort is being devoted in this area. 

Catalysis by solid surfaces is often very specific, however. The molecular architecture of the active patches is certainly a very important factor in catalysis. This may be accounted for by deformation of the molecules caused by the adsorption.3 Suppose, for instance, that the... 

Olah, G. A., Arvanaghi, M., Krishnamurthy, V. V. Heterogeneous catalysis by solid superacids. 17. Polymeric perfluorinated resin sulfonic acid (Nafion-H) catalyzed Fries rearrangement of aryl esters. J. Org. Chem. 1983,48, 3359-3360. 

Olah, G. A., Reddy, V. P., Prakash, G. K. S. Catalysis by solid superacids. 26. Peterson (silyl-Wittig) methylenation of carbonyl compounds using Nafion-H catalyzed hydroxy-trimethylsilane elimination of P-hydroxysilanes. Synthesis 1991,29-30. 

Previous sections have shown that catalysis by solid acids has received much attention due to its importance in petroleum refining and petrochemical processes. Conversely, relatively few studies have focused on catalysis by bases, even if acid and base are paired concepts. Base catalysts, however, play a decisive role in several reactions essential for fine-chemical syntheses [248-251]. Solid-base catalysts have many advantages over liquid bases. Examples of successfijl reactions include isomerization, aldol condensation, Knoevenagel condensation, Michael condensation, oxidation and Si—C bond formation. Various reviews have discussed catalysis by solid bases [248-255]. 

One of the oldest theories relating to catalysis by solid surfaces was proposed by Faraday in 1825. This states that adsorption of... 

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