Silica-alumina, amorphous, cracking

The Mobility of Silica in Steam. The reactivity of silica and silica-containing materials to steam has been assumed in the literature to explain several phenomena, a few of which are the sintering of silica (35), the aging of amorphous silica alumina cracking catalysts (36) and the formation of ultrastable molecular sieves (37). The basis of all these explanations is the interaction of siliceous materials with water to form mobile, low molecular weight silicon compounds by hydrolysis (38) such as ... 

Following their introduction to the refining industry in 1962, zeolite cracking catalysts, have virtually replaced the amorphous silica alumina cracking catalysts that had previously dominated the marketplace. To the rare earth industry the development of zeolite catalysts represented a new end use without precedent. Nearly all zeolite cracking... 

During the 1940,s, much effort was made to elucidate the nature of the active sites in amorphous silica-alumina cracking catalysts (11). By... 

To explain the observed selectivity effect, consider the type of mechanism proposed by Matsumoto et al (9, 10) for reactions of o-ethyltoluene with H+A102 of amorphous silica-alumina cracking catalysts. 

The catalytic conversion of -hexane was proposed in 1966 and 1980 as a test reaction for zeoUte catalysts by Mobil [80,116] and is nowadays used in the form of the so-called a test. The a activity is the ratio of the cracking rate constant for a given catalyst and the rate constant of an equal volume of a standard amorphous silica-alumina cracking catalyst... 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable.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. 

Zeolites as cracking catalysts are characterized hy higher activity and better selectivity toward middle distillates than amorphous silica-alumina catalysts. This is attrihuted to a greater acid sites density and a higher adsorption power for the reactants on the catalyst surface. 

Compared to amorphous silica-alumina catalysts, the zeolite catalysts are more active and more selective. The higher activity and selectivity translate to more profitable liquid product yields and additional cracking capacity. To take full advantage of the zeolite catalyst, refiners have revamped older units to crack more of the heavier, lower-value feedstocks. 

Table 9.5. Approximate product distributions of fluid catalytic cracking for amorphous silica-alumina and zeolite catalysts.

Although cracking also occurs on chlorine-treated clays and amorphous silica-aluminas, the application of zeolites has resulted in a significant improvement in gasoline yield. The finite size of the zeolite micropores prohibits the formation of large condensed aromatic molecules. This beneficial shape-selectivity improves the carbon efficiency of the process and also the lifetime of the catalyst. 

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. 

As mentioned earlier, fluid cracking catalyst are presently comprised of three principal ingredients, an amorphous silica-alumina refractory binder, a generally inert filler and the zeolite. 

C at pressures of about 250—400 kPa (36—58 psi). The two types of catalysts, the amorphous silica—alumina (52) and the crystalline aluminosilicates called molecular sieves or zeolites (53), exhibit strong carboniumion activity. Although there are natural zeolites, over 100 synthetic zeolites have been synthesized and characterized (54). Many of these synthetic zeolites have replaced alumina with other metal oxides to vary catalyst acidity to effect different type catalytic reactions, for example, isomerization. Zeolite catalysts strongly promote carboniumion cracking along with isomerization, disproportionation, cyclization, and proton transfer reactions. Because butylene yields depend on the catalyst and process conditions, Table 7 shows only approximations. 

Aluminosilicates are the active components of amorphous silica—alumina catalysts and of crystalline, well-defined compounds, called zeolites. Amorphous silica—alumina catalysts and similar mixed oxide preparations have been developed for cracking (see Sect. 2.5) and quite early [36,37] their high acid strength, comparable with that of sulphuric acid, was connected with their catalytic activity. Methods for the determination of the distribution of the acid sites according to their strength have been found, e.g. by titration with f-butylamine in a non-aqueous medium using adsorbed Hammett indicators for the H0 scale [38],... 

Andreu et ah (11) explained the increased activity (with increasing alumina content of amorphous silica-alumina catalysts) for cracking of sec-butylbenzene by the greater density of acid sites in the high-alumina-content catalysts. Adams et ah (12) proposed that the interaction of several active sites with reactant molecules in mordenite catalysts was partly responsible for the rapid rate of activity loss. 

Nor did catalytic cracking escape the probing attention of Paul Emmett. At Johns Hopkins his students used labeled molecules extensively to examine the nature of secondary reactions in the cracking of cetane over amorphous silica-alumina and crystalline zeolites. They demonstrated that small olefins (e.g., propylene) are incorporated extensively into higher-molecular-weight molecules, especially aromatics, and are the primary source of coke formation on these catalysts. 

Historically, the isomerization catalysts have included amorphous silica—aluminas, zeolites, and metal-loaded oxides. All of the catalysts contain acidity, which isomerizes the xylenes and if strong enough can also crack the EB and xylenes to benzene and toluene. Dual functional catalysts additionally contain a metal that is capable of converting EB to xylenes. 

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