Silica alumina catalysts activity

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. 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable.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

The breakthrough in FCC catalyst was the use of X and Y zeolites during the early 1960s. The addition of these zeolites substantially increased catalyst activity and selectivity. Product distribution with a zeolite-containing catalyst is different from the distribution with an amorphous silica-alumina catalyst (Table 4-3). In addition, zeolites are 1,000 times more active than the amorphous silica alumina catalysts. 

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

We carried out the reaction in a flow system under conditions such that the conversion level was high but well below equilibrium conversion. We used C.P. 1-butene from Matheson and passed it over 100-200 mesh Mobil silica-alumina catalyst [10% AljOj surface area, 393m g (BET)] the batch was heated 1 hr at 450°C in an air stream and kept in a closed container. Gas chromatographic analysis was used neither reactant impurity nor a thermal rate was found to be a complicating factor. The reaction was carried out at 120, 135, 150, and 165°C at several partial pressures, using N2 as diluent, up to 0.95 atm. The reactant flow rate was always 1.56 x 10" mole min A steady state was achieved in about 20 min, and the activity for a run was taken to be the average of three determinations made between 35 and 50 min. 

The rate of reaction of propylene over the MeReOs/HMDS/silica-alumina catalyst (1.4 wt% Re) is shown in Figure 2b. The profile is similar to that of the Sn-promoted perrhenate catalyst, with kobs = (1-78 + 0.09) x 10" s, and the activity responds similarly to subsequent additions of propylene. In fact, the pseudo-first-order rate constant for the organometallic catalyst lies on the same line as the rate constants for the Sn-promoted perrhenate catalyst. Figure 3. Therefore we infer that the same active site is generated in both organometallic and promoted inorganic catalyst systems. 

The influence of the surface polarity of powders on their adsorption and dispersion properties can be profound, as is discussed in Sec. VIII,A. The values of F are likely to be put to many uses as more of them are measured. The electrostatic surface fields are doubtless involved in the phenomena of chemisorption and catalysis, capable of inducing polarization or electron shift of adsorbing molecules. For silica-alumina catalysts, the production of active M-O-M surface groups must be considered the most important factor responsible for chemisorption and catalj ic activity. 

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],... 

It follows from all the above considerations that the acidic character of the surface is necessary for the esterification reaction. This view is supported by the parallel found by some workers [405,406] between the rate of esterification and that of other typical acid-catalysed reactions. A linear correlation was established between the rate of acetic acid—ethanol esterification and that of deisopropylation of isopropylbenzene on a series of silica—alumina, alumina—boria and alumina catalysts [406] a similar relation was found between the rate coefficient of the same esterification reaction and the cracking activity of a series of silica—alumina catalysts prepared in a different way [405]. 

To study the interaction of adsorbed molecules with active sites in decationized zeolites we used optical electronic spectroscopy, which was successful (17-19) with silica-alumina catalysts. The results (17-19) were then extrapolated to zeolites 20-21). 

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. 

Dehydration of ethanol has been effected over a variety of catalysts, among them synthetic and naturally occurring aluminas, silica-aluminas, and activated alumina (315—322), hafnium and zirconium oxides (321), and phosphoric acid on coke (323). Operating space velocity is chosen to ensure that the two consecutive reactions,... 

The distribution of A1 spedes of varying coordination (tetrahedral, pentacoordinated and octahedral) can be influenced by changing the conditions of hydrothermal pretreatment of amorphous silica-alumina catalysts. However, for a given composition, activity per unit surface area and selectivity were independent of pretreatment conditions. Thus, gas oil cracking activity and selectivity in amorphous silica-alumina cannot be... 

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