Crystalline high-alumina silica-aluminas

Table 2. RELATIVE STABILTIY OF AMORFHOUS AND CRYSTALLINE HIGH-ALUMINA SILICA ALUMINAS...

In addition to the crystalline clays described earlier, there are some materials that act like clays but do not have crystalline structure. Amorphous clays do not have a definite X-ray diffraction pattern and are differentiated from the crystalline clays on this basis. They are composed of mixtures of alumina, silica, and other oxides and generally have high sorptive and cation exchange capacities. Few soils contain large amounts of amorphous clays [2],... 

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],... 

Zeolites are crystalline aluminosilicates that have exhibited catalytic activities ranging from one to four orders of magnitude greater than amorphous aluminosilicates for reactions involving carbonium ion mechanisms such as catalytic cracking (144). As a result extensive efforts have been undertaken to understand the nature of the catalytic sites that are responsible for the observed high activity. The crystalline nature of zeolites permits more definite characterization of the catalyst than is possible for amorphous acidic supports such as alumina and silica-alumina. Spectral techniques, in conjunction with structural information derived from X-ray diffraction studies, have led to at least a partial understanding of the nature of the acidic sites in the zeolite framework. 

Nickel and vanadium are contained within the crude oil as their respective porphyrins and napthenates (2). As these large molecules are cracked, the metals are deposited on the catalyst. Nickel which possesses a high intrinsic dehydrogenation and hydrogenolysis activity drastically increases the production of coke and dry gas (particularly H2) at the expense of gasoline. Vanadium on the other hand interacts with the zeolitic component of a cracking catalyst and leads to destruction of its crystallinity. This results in reduced activity as well as an increase in non-selective amorphous silica-alumina type cracking. Supported vanadium also has an intrinsic... 

Zeolites, crystalline alumina silicates with open regular structure, oiFer unusual opportunities for carrying out catal3rtic studies. Their well-defined crystalline structure and their regular pore distribution permit a better description of the surface than that offered by alumina-silica gel catalysts. Consequently, in recent years they have been the object of many scientific investigations. In addition, zeolites of a variety of types have shown highly desirable properties in industrial catalysis (1.2). This chapter is a review of the work on zeolites carried out at Princeton University and is not intended to be an exhaustive review of the topic. 

Studies of catalysts deactivation by coke are abundant in the literature most of them are usually conducted at high temperatures (around 500°C) using metal catalysts supported on oxides with low surface area such as silica, aluminas or silica-alumina [2 and references therein]. The deactivation by coke of zeolite catalysts has also been studied and such studies have mostly been done for high temperature reactions such as the conversion of n-hexane or the isomerization of xylenes [2,4]. However, low temperature coke formation (20-25°C) combining the effect of high acidity and size specificity for a high coking component such as nickel, has not yet been considered from the point of view of the presence of compounded effects of crystalline structure and location of metal particles. 

The structural stability of a Variety of commercially available hydrothermally dealuminated Y type zeolites in high pH ammonium salt solutions was studied It was found that such zeolites can lose large amounts of crystallinity, the susceptibility to structure loss increasing with salt concentration and pH, and with increases in both the chemical and framework silica/alumina ratio of the zeolite,... 

Zeolites were selected for these studies because they possessed the types of properties (high crystallinity, low sodium content, and wide range of silica/alumina ratio) generally valued in catalyst development work All were commercial (not developmental) products of either the Linde Division of Union Carbide Corporation (Danbury, Connecticut) or Conteka, B.V. (Surte, Sweden). 

The higher the active surface area of the catalyst, the greater the number of product molecules produced per unit time. Therefore, much of the art and science of catalyst preparation deals with high-surface-area materials. Usually materials with 100- to 400-m /g surface area are prepared from alumina, silica, or carbon and more recently other oxides (Mg, Zr, Ti, V oxides), phosphates, sulfides, or carbonates have been used. These are prepared in such a way that they are often crystalline with well-defined microstructures and behave as active components of the catalyst system in spite of their accepted name supports. Transition-metal ions or atoms are then deposited in the micropores, which are then heated and reduced to produce small metal particles 10-10" A in size with virtually all the atoms located on the surface... 

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