Clay catalyst, activated structure

Kaolin had little or no cracking activity, and catalyst activity as tested in the laboratory was directly related to silica-alumina gel content. However, the catalyst performed much better in commercial tests than anticipated from laboratory testing. Undoubtedly, this open structure encountered much less severe conditions at the outer surface of the microsphere during regenerations and made internal catalytic surfaces more readily available. This first of the so-called "semisynthetics" was called Nalco 783, and the matrix is still used in many forms some 28 years later.(7,13) Today it is estimated that some 200,000 tons/yr. of kaolin clay is used for cracking catalyst manufacture as reported by Georgia Kaolin Corporation.(24) Figure 10 shows the pore volume distribution for Nalco 783 and two other commercial semisynthetics from that period. 

The activity advantage of zeolite catalysts over amorphous silica-alumina has well been documented, Weisz and his associates [1] reported that faujasite Y zeolite showed 10 to 10 times greater activity for the cracking of n-hexane than silica-alumina. Wang and Lunsford et al. [2] also noted that acidic Y zeolites were active for the disproportionation of toluene while silica-alumina was inactive. The activity difference between zeolite and silica-alumina has been attributed to their acidic properties. It is, however, difficult to explain the superactivity of zeolite relative to silica-alumina on the basis of acidity, since the number of acid sites of Y-type zeolite is only about 10 times larger than that of silica-alumina. To account for it, Wang et al. [2] proposed that the microporous structure of zeolite enhanced the concentration of reactant molecules at the acid sites. The purpose of the present work is to show that such a microporous effect is valid for pillared clay catalysts. 

With fresh activated-clay catalyst, endothermic peaks are observed at temperatures of about 300, 1200, and 1600°F. These three peaks are attributed to loss of physically adsorbed water, loss of chemically bound (hydroxyl) water, and collapse of the montmorillonite structure, respectively. The hydroxyl water originally present amounts to 3 or 4%. The magnitude of the peak at 1200°F. decreases if the sample is heated above 800°F. prior to thermal analysis, and disappears completely if the sample is calcined at 1100°F. The thermal-analysis curve for the dehydrated catalyst is flat up to the point at which the montmorillonite structure begins to disappear. If the catalyst has not been heated above 1450°F., it becomes rehydrated upon exposure to moisture and a new endothermic peak appears in the curve between 800 and 1000°F. The size of the new peak increases as that of the original hydroxyl-water peak decreases it corresponds to 1.5 to 2.0% sorbed water with catalyst that has been rehydrated after calcination at 1100°F. The rehydration capacity of the catalyst decreases as the catalyst becomes partially deactivated with use. 

Other examples are pillared bentonite and other clays, which exist as thin sheets only weakly connected, if at all. These layered materials yield low levels of LCB when the catalyst activated at temperatures below its fusion temperature. However, if it is heated to 600-700 °C, so that the structure rearranges, very high LCB levels are produced in the polymer. 

Dimerization.—Unsaturated acids, whether monoenoic or polyenoic, furnish dimers which are in demand because of the valuable surface-active properties of their various derivatives. Methods of dimerization have therefore been extensively examined, but understanding of the reaction and the structural identification of the products have lagged behind. Dimerization is effected in several ways but clay catalysts are the most widely employed, and it is now recognized that such catalysts operate in several ways. They may promote modification of monoenoic and dienoic acids to more reactive monomers in addition to assisting both the dimerization process and the subsequent changes in the dimer molecules. In particular, hydrogen transfer seems to be important monoenoic acids are thereby converted to more reactive dienoic acids and the dimer (probably a cyclohexene derivative resulting from Diels-Alder reaction) is converted to a substituted aromatic compound. ... 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable. Incorporating zeolites (crystalline alumina-silica) with the silica/alumina catalyst improves selectivity towards aromatics. These catalysts have both Fewis and Bronsted acid sites that promote carbonium ion formation. An important structural feature of zeolites is the presence of holes in the crystal lattice, which are formed by the silica-alumina tetrahedra. Each tetrahedron is made of four oxygen anions with either an aluminum or a silicon cation in the center. Each oxygen anion with a -2 oxidation state is shared between either two silicon, two aluminum, or an aluminum and a silicon cation. 

Dimerization of unsaturated fatty acids, to. so-called dimer acids, is widely practised in industry, where acid-treated clays are invariably used as a catalyst. In the case of oleic acid the major products are dimers, trimers, and isosteric acid. Koster et al. (1998) have investigated the relative importance of the various acid sites as well as structural and textural parameters of montmorrilonite. The interlamellar space dominates the oleic acid dimerization and the active site is the tetrahedrol substitution site. 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

A recent investigation has demonstrated the usefulness of ultrasonic irradiation in the preparation of delaminated zeolites, which are a particular type of modified oxides - microporous crystalline aluminosilicates with three-dimensional structures - having a greater catalytic activity than the layered structures (clays) and mesoporous catalysts. In an attempt to increase the pore size of zeolites, a layered zeolite precursor was... 

Recently, interest in clays as acidic catalysts has been quickened by the reported high catalytic activity of a synthetic mica-montmorillonite clay and its nickel-containing analogs. Wright et al. (247) have described the structure, thermal modification and surface acidity of the clay, which they designated SMM for synthetic mica-montmorillonite. 

Strong mineral acids react with clays to hydrolyze aluminum-oxygen bonds. The aluminum dissolves, leaving an altered structure. Protons in the acid also exchange with sodium and other alkali cations, leaving an acidic material. Houdry took advantage of such reactions in making the active acidic catalysts... 

The inherent limitations of the use of zeolites as catalysts, i.e. their small pore sizes and long diffusion paths, have been addressed extensively. Corma reviewed the area of mesopore-containing microporous oxides,[67] with emphasis on extra-large pore zeolites and pillared-layered clay-type structures. Here we present a brief overview of different approaches to overcoming the limitations regarding the accessibility of catalytic sites in microporous oxide catalysts. In the first part, structures with hierarchical pore architectures, i.e. containing both microporous and mesoporous domains, are discussed. This is followed by a section on the modification of mesoporous host materials with nanometre-sized catalytically active metal oxide particles. 

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