Alumina-silica

1 Polyethylene - The degradation of polyethylene has been most widely studied in the presence of amorphous silica-alumina (SA) 

These results are in contrast to the results of Beltrame et al. who carried out the degradation of co-milled polyethylene and two different silica-alumina catalysts with alumina contents of 24.2 and 13.2 wt%. ° At the same temperature used by Ohkita et al., i.e. 673 K, the degradation resulted in the evolution of over 90 wt% oils, less than 8 wt% gas and negligible amounts of residue.However, it is important to note the differences in the reactor configurations used in these two 

Ishihara et al. also carried out decomposition of polyethylene at 703 K over a silica-alumina catalyst with 13 wt% alumina but used a fixed bed reactor and a low density reactant. In their experiments, 72 wt% of the products were gaseous, while only 15 wt% of the products were liquids. Only 7 wt% gaseous products were formed without the catalyst present. However, the product yields were a strong function of residence time in the system. As the residence time was varied from 2.2 to 13.2 s, the gas yield passed through a maximum at 4.7 s 

To address the deactivation behavior in more detail, Uemichi et al. recently examined the change in activity of a silica-alumina catalyst with 13 wt% alumina as a function of time on stream. At a reaction temperature of 723 K, the SA catalyst accumulated over 12 wt% coke on the catalyst after 250 min time on stream. The liquid yield increased slightly from 60 wt /o to approximately 70 wt% as the coke built up on the catalyst. The limited effect of the coke on the reaction was attributed to the inability of coke deposits to block completely the large pores (f/p,ave = 4.4 nm) of the amorphous catalyst. Although SA showed no activity toward cracking of -octane, the reactivity of polyethylene was substantially enhanced in the presence of the catalyst. This was attributed to the facile reaction on the catalyst of olefins which could be formed from thermal degradation of polyethylene at the temperatures used in this study. 

2 Polypropylene - The studies of degradation of polypropylene in the presence of silica-alumina are more limited than those examining polyethylene. Because of the tertiary centers along the polymer 

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Many solids have foreign atoms or molecular groupings on their surfaces that are so tightly held that they do not really enter into adsorption-desorption equilibrium and so can be regarded as part of the surface structure. The partial surface oxidation of carbon blacks has been mentioned as having an important influence on their adsorptive behavior (Section X-3A) depending on conditions, the oxidized surface may be acidic or basic (see Ref. 61), and the surface pattern of the carbon rings may be affected [62]. As one other example, the chemical nature of the acidic sites of silica-alumina catalysts has been a subject of much discussion. The main question has been whether the sites represented Brpnsted (proton donor) or Lewis (electron-acceptor) acids. Hall... 

The analysis is thus relatively exact for heterogeneous surfaces and is especially valuable for analyzing changes in an adsorbent following one or another treatment. An example is shown in Fig. XVII-24 [160]. This type of application has also been made to carbon blacks and silica-alumina catalysts [106a]. House and Jaycock [161] compared the Ross-Olivier [55] and Adamson-Ling... 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Acids are not limited to liquid (or gaseous) systems. Solid acids also play a significant role. Acidic oxides such as silica, silica-alumina, etc. are used extensively as solid acid catalysts. New solid acid systems that are stronger than those used conventionally are frequently called solid superacids. 

Fig. 2.8 The adsorption of nitrogen at 77 K on nonporous samples of silica and alumina, ranging from 2-6 to 11-5 m g for silica and from 58 to 153m g for alumina. n/n is plotted against pjp°. (A) O, silica , alumina. (B) BET isotherm (Equation 2.12) with c values of 100-2(X).

Amorphous Silica—Alumina Based Processes. Amorphous siHca—alumina catalysts had been used for many years for xylene isomerization. Examples ate the Chevron (130), Mamzen (131), and ICI (132—135). The primary advantage of these processes was their simpHcity. No hydrogen was requited and the only side reaction of significance was disproportionation. However, in the absence of H2, catalyst deactivation via coking... 

Table 14-16 lists t)pical grades of porous carbon, silica, alumina, stainless steel (t)pe 316y and polymers commercially available. 

Strong acids are able to donate protons to a reactant and to take them back. Into this class fall the common acids, aluminum hahdes, and boron trifluoride. Also acid in nature are silica, alumina, alumi-nosihcates, metal sulfates and phosphates, and sulfonated ion exchange resins. They can transfer protons to hydrocarbons acting as weak bases. Zeolites are dehydrated aluminosilicates with small pores of narrow size distribution, to which is due their highly selective action since only molecules small enough to enter the pores can reacl . 

Cracking, a rupturing of carbon-carbon bonds—for example, of gas oils to gasohne—is favored by sihca-alumina, zeolites, and acid types generally. Zeohtes have pores with small and narrow size distribution. They crack only molecules small enough to enter the pores. To restrain the undesirable formation of carbon and C3-C4 hydrocarbons, zeolite activity is reduced by dilution to 10 to 15 percent in silica-alumina. 

Dehydration and dehydrogenation combined utihzes dehydration agents together with mild dehydrogenation agents. Included in this class are phosphoric acid, sihca-magnesia, silica-alumina, alumina derived from aluminum chloride, and various metal oxides. 

Isomerization is promoted by either acids or bases. Higher alkylbenzenes are isomerized in the presence of AlCb/HCl or BF3/HF olefins with most mineral acids, acid salts and silica-alumina saturated hydrocarbons with AlCb or AlBr,3 promoted by 0.1 percent of olefins. 

Take the silica-alumina system as an example. It is convenient to treat the components as the two pure oxides SiOj and AI2O3 (instead of the three elements Si, A1 and O). Then the phase diagram is particularly simple, as shown in Fig. 16.6. There is a compound, mullite, with the composition (Si02)2 (Al203)3, which is slightly more stable than the simple solid solution, so the alloys break up into mixtures of mullite and alumina, or mullite and silica. The phase diagram has two eutectics, but is otherwise straightforward. 

In particular, emphasis will be placed on the use of chemisorption to measure the metal dispersion, metal area, or particle size of catalytically active metals supported on nonreducible oxides such as the refractory oxides, silica, alumina, silica-alumina, and zeolites. In contrast to physical adsorption, there are no complete books devoted to this aspect of catalyst characterization however, there is a chapter in Anderson that discusses the subject. 

The preferred catalyst is one which contains 5% of chromium oxides, mainly Cr03, on a finely divided silica-alumina catalyst (75-90% silica) which has been activated by heating to about 250°C. After reaction the mixture is passed to a gas-liquid separator where the ethylene is flashed off, catalyst is then removed from the liquid product of the separator and the polymer separated from the solvent by either flashing off the solvent or precipitating the polymer by cooling. 

A hydrated silica-alumina compound, associated with ferric oxide. Used as a filter medium and as a catalyst and catalyst carrier and in cosmetics and insecticides. 

Titanium dioxide used for adhesive applications should contain an inorganic coating to control polarity, improve its ease of dispersion, and improve its weather resistance. The inorganic coating (zirconium dioxide, silica, alumina) is applied in the aqueous sluny by precipitation of one or more hydrated metal oxides and by neutralization of acidic and alkaline compounds. 

Inorganic packings (silica, alumina, etc.) are very stable (yet brittle) and show very high pore volumes (i.e, efficiency). However, their chemical stability is very limited and the surface is very active (this is also true for reversed-phase columns), allowing their use in special applications only. 

Pyridinium / -toluenesulfonate, 5°, 1 h." Similar selectivity can be achieved using a silica-alumina gel prepared by the solgel method. ... 

A great many materials have been used as catalyst supports in hydrogena-tion, but most of these catalyst have been in a quest for an improved system. The majority of catalyst supports are some form of carbon, alumina, or silica-alumina. Supports such as calcium carbonate or barium sulfate may give better yields of B in reactions of the type A- B- C, exemplified by acetylenes- cjs-olefins, apparently owing to a weaker adsorption of the intermediate B. Large-pore supports that allow ready escape of B may give better selectivities than smaller-pore supports, but other factors may influence selectivity as well. 

The allcylation of a number of aromatic compounds through the use of a chloroa-luminate(III) ionic liquid on a solid support has been investigated by Holderich and co-workers [87, 88]. Here the allcylation of aromatic compounds such as benzene, toluene, naphthalene, and phenol with dodecene was performed using the ionic liquid [BMIM]C1/A1C13 supported on silica, alumina, and zirconia. With benzene, monoalkylated dodecylbenzenes were obtained (Scheme 5.1-56). 

Adsorption processes use a solid material (adsorbent) possessing a large surface area and the ability to selectively adsorb a gas or a liquid on its surface. Examples of adsorbents are silica (Si02), anhydrous alumina (AI2O3), and molecular sieves (crystalline silica/alumina). Adsorption processes may be used to remove acid gases from natural gas and gas streams. For example, molecular sieves are used to dehydrate natural gas and to reduce its acid gases. 

Isomerization of alkylcyclopentanes may also occur on the platinum catalyst surface or on the silica/alumina. For example, methylcyclopen-tane isomerizes to cyclohexane ... 

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. 

The product distrihution is influenced hy the catalyst properties as well as the various reaction parameters. The catalyst activity and selectivity are functions of acidity, crystalline size, silica/alumina ratio, and even the synthetic procedure. Since the discovery of the MTG process. 

Other catalyst systems such as iron V2O5-P2O5 over silica alumina are used for the oxidation. In the Monsanto process (Figure 6-4), n-butane and air are fed to a multitube fixed-bed reactor, which is cooled with molten salt. The catalyst used is a proprietary modified vanadium oxide. The exit gas stream is cooled, and crude maleic anhydride is absorbed then recovered from the solvent in the stripper. Maleic anhydride is further purified using a proprietary solvent purification system. ... 

High-density polyethylene (HDPE) is produced by a low-pressure process in a fluid-bed reactor. Catalysts used for HDPE are either of the Zieglar-type (a complex of A1(C2H5)3 and a-TiCl4) or silica-alumina impregnated with a metal oxide such as chromium oxide or molybdenum oxide. 

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