Zeolites modified, catalysts

Reaction conditions 0.1 g of the zeolite Y modified catalyst, tested in a conventional glass microreactor with racemic butan-2-ol (7.35 x 10" mol h-1), prevaporized in a nitrogen diluent (6.2 -6.7 x 10" mol h-1). Products were analyzed using on-line GC with a 40m capillary y- cyclodextrin colimm with trifluoroacetyl stationary phase, temperature programmed from 25-70 "C with a split ratio of 120 1. 

The analysis of the literature data shows that zeolites modified with nobel metals are among perspective catalysts for this process. The main drawbacks related to these catalysts are rather low efficiency and selectivity. The low efficiency is connected with intracrystalline diffusion limitations in zeolitic porous system. Thus, the effectiveness factor for transformation of n-alkanes over mordenite calculated basing on Thiele model pointed that only 30% of zeolitic pore system are involved in the catalytic reaction [1], On the other hand, lower selectivity in the case of longer alkanes is due to their easier cracking in comparison to shorter alkanes. 

Isomerization of olefins or paraffins is an acid-catalyzed reaction that can be carried out with any number of strong acids, including mineral acids, sulfated metal oxides, zeolites and precious metal-modified catalysts [10]. Often the catalyst contains both an acid function and a metal function. The two most prevalent catalysts are Pt/chlorided AI2O3 and Pt-loaded zeolites. The power of zeoHtes in this reaction type is due to their shape selectivity [11] and decreased sensitivity to water or other oxygenates versus AICI3. It is possible to control the selectivity of the reaction to the desired product by using a zeoHte with the proper characteristics [12]. These reactions are covered in more detail in Chapter 14. 

Alkali metal ion-exchanged zeolites and occluded alkali metal oxide zeolites have been investigated extensively and applied as basic catalysts for a variety of organic transformations (1,41,221,222). Zeolites modified with alkaline earth compounds have been applied much less frequently as base catalysts for organic reactions. 

Because BaO/NaX zeolite catalysts exhibited the best performance, further investigations have been carried out recently to characterize the oxidative methylation of toluene catalyzed by BaO-modified X- and Y-zeolites, mordenite, ZSM-5, sil-icalite, and ALPO4-5 (230). The authors found that activity and basicity of BaO-modified zeolites and zeolite-like catalysts depend on both the structural type and composition. Thus, for samples of the same structural type (BaO/NaX zeolite. 

Transesterification Reactions. The heterogeneous acid-catalyzed transesterification of TGs has not been investigated as much as its counterpart, the base-catalyzed reaction. Various solids are available with sufficient acid strength to be effective catalysts for the named reaction. Among the solid acids available are functionalized polymers, such as the acid forms of some resins, as well as inorganic materials, such as zeolites, modified oxides, clays, and others. Some of these solids have already been found to be effective in transesterification reactions of simple esters and (3-ketoesters. 

Feolite catalysts modified by transition metals are interesting and difficult subjects to study. In one of the first studies of zeolites as catalysts, Rabo and co-workers (1) used a zeolite catalyst containing 0.5% platinum for isomerization of n-paraffins. In this reaction the metal-zeolite system acted as a typical representative of the bifunctional catalysts. Studies of zeolites modified by transition metals ( 2, 3, Jf) showed that their polyfunctional properties are determined by the structural and chemical properties of the zeolite and by the state of the metal in it. In this paper we discuss new data on the metal state after reduction as well as the catalytic functions of zeolite catalysts containing nickel and platinum. 

In this paper, the results of the isomerization of hexane, heptane and octane over a Mo2C-oxygen-modified-catalyst, a Mo03-carbon-modified catalyst and a Pt//l-zeolite catalyst, at atmospheric pressure, are presented. Also, the results for a conventional Pt/Al203 catalyst are presented for the isomerization of hexane. Then, the effect of pressure on the isomerization of heptane and octane over the molybdenum catalysts and the Pt//l-zeolite catalyst is shown. Finally, the ability of the molybdenum catalysts to catalyse the isomerization reaction at high conversion with high selectivity even with hydrocarbons larger than hexane is demonstrated this is not possible over the Pt catalysts. The differences between the catalysts are discussed in terms of the reaction mechanisms. 

Comparison of the activity over the Mo03-carbon-modified catalyst, which as already mentioned, is the most active of the molybdenum catalysts, with that obtained for the Pt// -zeolite shows that the platinum is... 

The effect of pressure on the isomerization of n-heptane and n-octane was determined over the Pt//l-zeolite, Mo2C-oxygen-modified and M0O3-carbon-modified catalysts. The weight hour space velocity (WHSV) was changed with the pressure to keep the conversion at a similar level, enabling the effect on the isomerization selectivity and the product distributions to be seen. Other conditions were kept constant. 

Pt// -zeolite, Mo2C-oxygen-modified and Mo03-carbon-modified catalysts leads to a decrease in the ratio of the M2H/M3H isomers of 1.10 to 1.02, 0.92 and 0.87 to 0.71 respectively. 

Since differences in the hydrogenation rates of variously substituted monoalkenes were found over Pt-zeolite catalysts modified by CVD (see Section IV.A.l) these catalysts were anticipated to exhibit regioselectivities in the hydrogenation of dienes. Selective saturation of the less substituted double bonds of linear and cyclic dienes was indeed achieved over Pt-zeolite A and Rh-zeolite A catalysts treated with tetraethoxysilane78 or diethoxydiphenylsilane79,80 (Table 13). 

Nitrous oxide offers a tempting possibility for the epoxidation of propylene and butylene in the gas phase. Encouraging results were obtained with Fe-modified Si02 and some zeolite-like catalysts. No other oxidant allows selective performance of these delicate reactions. 

Recently Mikae et al. (66) showed that NaY zeolite impregnated with NaCl solution can be used as a para selective catalyst for chlorination of chlorobenzene, which is indeed another example of zeolite modified advantageously by means of monolayer dispersion of salts. 

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