Silica-alumina catalyst acidity

The way in which the proton is associated with the alumina-silica catalyst is a matter of some doubt. Thomas (78) assumes the aluminium to be tetrahedral when linked with tetrahedral silicon, the extra valence electron being supplied by hydrogen from water contained in the catalyst (Fig. 21a). Both aluminium hydroxide and silicic acid are very weak acids because of the affinity of oxygen for the hydrogen (83), and a coordination of aluminium with the hydroxyl oxygen contained in the catalysts... 

Oblad, Milliken, and Mills (28) were among the first chemists to be fully aware of the chemical significance of surface stresses in catalysis. They explained the extremely high value for the heat of hydration of a thoroughly degassed alumina-silica catalyst on the basis of stresses. The author prefers to describe a system under tensile stress as acidic because of the incompletely screened cations. Using intemuclear distances and the screening demands of cations to describe the difference in surface films carries the macroscopic description of a solid under tension into the atomic dimensions (36). 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable.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

Catalyst acid properties depend on several parameters, including method of preparation, dehydration temperature, silica-to-alumina ratio, and the ratio of Bronsted to Lewis acid sites. 

In addition to this work on charcoal- and silica-supported catalysts and on evaporated platinum films, a number of studies have been made on alumina-supported platinum catalysts (e.g., 111-114, 81,115) in which the aim has been the study of reactions at the platinum alone. In these cases, one cannot automatically dismiss the possibility of participation of the alumina support (i.e., of dual function behavior of the catalyst) because it is known that alumina may have acidic properties, particularly when retained halogen is present. In general terms, there is no immediate answer to this problem because the nature of this sort of catalyst wall be much dependent on the details of catalyst history, preparation, and use. However, there can be little doubt that in many experimental studies using plati-num/alumina, and in which the assumption has been made that the alumina support is inert, this assumption is essentially valid. For instance, one may note the inert alumina used by Davis and Venuto (111) and the justification provided by Gault et al. (116) for the inertness of the alumina used in a substantial body of previous work irrespective of whether the catalyst was... 

Alumina, silica, clays, and zeolites are increasingly used as acidic or basic supports [26], Cycloaddition reactions often require Lewis-acid catalysts if good yields are to be obtained. Clay and doped silica gel catalysts have emerged as useful alternatives to the use of Lewis acids. Cycloaddition offuran (5) under solvent-free conditions, catalyzed by K10 montmorillonite, results in a decrease in the reaction time the endo-exo relationship is no different that obtained by use of classical heating (Scheme 9.2) [27]. 

Ethanol can be derived from biomass by means of acidic/enzymatic hydrolysis or also by thermochemical conversion and subsequent enzymatic ethanol formation. Likewise for methanol, hydrogen can be produced from ethanol with the ease of storage/transportation and an additional advantage of its nontoxicity. Apart from thermodynamic studies on hydrogen from ethanol steam reforming,117-119 catalytic reaction studies were also performed on this reaction using Ni-Cu-Cr catalysts,120 Ni-Cu-K alumina-supported catalysts,121 Cu-Zn alumina-supported catalysts,122,123 Ca-Zn alumina-supported catalysts,122 and Ni-Cu silica-supported catalysts.123... 

During the period 1940-1962, the cracking catalysts used most widely commercially were the aforementioned acid-leached clays and silica-alumina. The latter was made in two versions low alumina (about 13% AI2O3) and high alumina (about 25% AI2O3) contents. High-alumina-content catalysts showed a higher equilibrium activity level and surface area. 

Note that ethylbenzene is a derivative of two basic organic chemicals, ethylene and benzene. A vapor-phase method with boron trifluoride, phosphoric acid, or alumina-silica as catalysts has given away to a liquid-phase reaction with aluminum chloride at 90°C and atmospheric pressure. A new Mobil-Badger zeolite catalyst at 420°C and 175-300 psi in the gas phase may be the method of choice for future plants to avoid corrosion problems. The mechanism of the reaction involves complexation of the... 

The catalyst must also have acidity in the matrix in order to reduce the molecular weight of molecules too large to enter the zeolite and in order to also convert heavy-cycle oil to light-cycle oil. Our studies have established that good balance in acidity between the matrix and the zeolite tends to enhance selectivity. A stable matrix acidity is also required, and here a high alumina silica-alumina cogel was selected due to its demonstrated stability in the pre-zeolite era. Certainly many other acidic matrices could probably be substituted. 

Friedel-Crafts catalysts and hydrogen halides, protic acids, silica-alumina-type catalysts, or other protic catalysts are effective. 

In addition to large-scale industrial applications, solid acids, such as amorphous silica-alumina, zeolites, heteropoly acids, and sulfated zirconia, are also versatile catalysts in various hydrocarbon transformations. Zeolites are useful catalysts in fine-chemical production (Friedel-Crafts reactions, heterosubstitution).165-168 Heteropoly compounds have already found industrial application in Japan, for example, in the manufacture of butanols through the hydration of butenes.169 These are water tolerant, versatile solid-phase catalysts and may be used in both acidic and oxidation processes, and operate as bifunctional catalysts in combination with noble metals.158,170-174 Sulfated zirconia and its modified versions are promising candidates for industrial processes if the problem of deactivation/reactivation is solved.175-178... 

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. 

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,... 

Ethylamines. Mono-, di-, and triethyl amines, produced by catalytic reaction of ethanol with ammonia (330), are a significant oudet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, silica, or silica—alumina.. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethyl amine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give IV-ethylpiperidine [766-09-6] (332). 

The spectrum of ammonia chemisorbed on a silica-alumina cracking catalyst was studied to determine whether the acidity of these catalysts is due to a Lewis (nonprotonic) or a Bronsted type of acid (28, 29). This work was based on the premise that ammonia chemisorbed on Lewis sites would retain a NH3 configuration while ammonia chemisorbed on a Bronsted site would form NHt. The NH3 configuration was expected to have bands near 3.0 and 6.1 p and the NHt near 3.2 and 7.0 p. 

The acid function of the catalyst is supplied by the support. Among the supports mentioned in the literature are silica-alumina, silica-zirconia, silica-magnesia, alumina-boria, silica-titania, acid-treated clays, acidic metal phosphates, alumina, and other such solid acids. The acidic properties of these amorphous catalysts can be further activated by the addition of small proportions of acidic halides such as HF, BF3, SiFit, and the like (3.). Zeolites such as the faujasites and mordenites are also important supports for hydrocracking catalysts (2). 

The relationship between the two catalytic components is quite complex. Interactions between the support and the hydrogenation component can alter this relationship. For example, Larson et- al. (6) showed that, with platinum on silica-alumina, a selective adsorption of platinum by acid sites causes a reduction in catalyst acidity. Similarly, nickel reacts with the acid sites on silica-alumina forming nickel salts of the silica-alumina acid sites. It has been suggested (J) that one of the effects of sulfiding a nickel on... 

The processes described below are the evolutionary offspring of the fluid catalytic cracking and the residuum catalytic cracking processes. Some of these newer processes use catalysts with different silica/alumina ratios as acid support of metals such as Mo, Co, Ni, and W. In general the first catalyst used to remove... 

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