Water with zeolites

Tihe presence of exchangeable cations, framework oxygens, cavities of A different sizes, and previously adsorbed water molecules makes the interaction of water with zeolites complicated (1). As a result, in zeolites, water molecules with different physical properties exist, from tightly bound to liquid-like water. This was shown by NMR measurements (2,3 4) ... 

Many reactions in the fine-chemical industry are performed with organic liquids or in organic solvents. When the surface of a solid-acid catalyst is hydrophilic, the presence of small amounts of water can completely block the surface of the catalyst. Carefully dried catalysts and reagents must then be employed. It may be noted that zeolites with a high silica-to-alumina ratio are hydrophobic. The (internal) surface of the zeolite is, therefore, not readily poisoned by accumulation of (traces of) water. With zeolites, moreover, use can be made of the uniform size of the pores to perform shape-selective reactions after passivation of the catalytic sites on the external surface of the zeolite crystallites. In the bulk-chemical industry several interesting reactions have been developed with zeolite catalysts [27] (cf. the review of Tanabe and Hdlderich [28]). 

The main calorimetric studies on adsorption of water and ammonia on TS-1 and silicalite-1 have been reported by Bobs et al. [64,83,84,86], while other contributions came from the Auroux group [92] and Janchen et al. [93]. Cor-ma s group has investigated the interaction of water on zeolite [39]. The most important conclusion from the available literature is that calorimetric data require a very careful analysis, as probe molecules interact both with the silanols of the internal hydroxyl nests (see Sect. 3.8) and with Ti(lV) species. 

The concept of extractive reaction, which was conceived over 40 years ago, has connections with acid hydrolysis of pentosans in an aqueous medium to give furfural, which readily polymerizes in the presence of an acid. The use of a water-immiscible solvent, such as tetralin allows the labile furfural to be extracted and thus prevents polymerization, increases the yield, and improves the recovery procedures. In the recent past an interesting and useful method has been suggested by Rivalier et al. (1995) for acid-catalysed dehydration of hexoses to 5-hydroxy methyl furfural. Here, a new solid-liquid-liquid extractor reactor has been suggested with zeolites in protonic form like H-Y-faujasite, H-mordenite, H-beta, and H-ZSM-5, in suspension in the aqueous phase and with simultaneous extraction of the intermediate product with a solvent, like methyl Aobutyl ketone, circulating countercurrently. 

Krossner, M., Sauer, J., 1996, Interaction of Water With Brpnsted Acidic Sites of Zeolite Catalysts. Ab Initio Study of 1 1 and 2 1 Surface Complexes , J. Phys. Chem., 100, 6199. 

The sorption pumps are clean but are one shot , that is, two pumps in parallel and connected by valves alternatively are needed for a continuous pumping. When the first pump is saturated, the second pump is started, while the first is regenerated removing the liquid nitrogen, the trapped gas is expelled through the blow-off valve. The pump (with zeolite) is heated to 200-300°C to remove water vapour. Charcoal pumps are heated to about 100°C. 

This work prompted a flurry of activity in the mid- to late 1980s to find the type IM isotherm. A number of inventions can be found in which alumina, or silica gel are blended with zeolites type X or Y to mimic the shape of the isotherm that Collier defined. Mol Sieve type DDZ-70(g) is in fact one of only a few true type IM isotherms. This product and Engelhard s type ETS-10 both have the required isotherm shape for water and deliver the benefits expected, to wit excellent capacity for water, self-sharpening mass transfer zone and low energy investment required to regenerate. Mol Sieve type DDZ-70(g) is used commercially in rotors... 

With zeolites as the solid acid catalyst, the best results for HMF synthesis were obtained by Moreau et al. who tested acidic mordenites with different Si/Al ratios in batch experiments and reported that dealuminated H-Mordenite with Si/Al ratio of 11 exhibited the highest selectivity and even so at reasonably high fructose conversion (91% selectivity at 76% conversion after 60 min. at 165 °C using water/methyl isobutyl ketone as the reaction media).Other zeolites, H-Y, H-Beta and H-ZSM-5 were also tested for the reaction, however, none of these catalysts were as selective as H-mordenite. ... 

Numerous processes have been proposed for extracting potash from felspar, leucite, alunite, and other minerals rich in this substance, but the cost is so great that very few proposals yet made ofier promise of successful competition with the Stassfurt deposits. This is even the case with alunite, where mere calcination to 1000° drives off water and sulphuric acid, leaving water-soluble potassium sulphate, and alumina. Humphry Davy in his paper On Some Chemical Agencies of Electricity (1807), indicated in Cap. Ill, found that when water was electrolyzed in cavities contained in celestine, fluorspar, zeolite, lepidolite, basalt, vitreous lava, agate, or glass, the bases separated from the acid and accumulated about the cathode. It is therefore probable that if water with finely divided potash minerals in suspension were electrolyzed, the alkali would be separated in a convenient simple way. 

Physicochemical properties of L zeolites and of clinoptilolite were studied by adsorption, chromatographic, spectral, and ther-mogravimetric methods. The sodium form of L zeolite is characterized by better adsorption with respect to water and benzene vapor and by higher retention volumes of C C hydrocarbons and CO than potassium and cesium forms. The activation energy of dehydration determined by the thermogravimetric method decreases on going from the sodium to cesium form of L zeolite. When calcium is replaced by potassium ions in clinoptilolite, the latter shows a decreased adsorption with respect to water vapor. The infrared spectra of the L zeolite at different levels of hydration show the existence of several types of water with different bond characters and arrangements in the lattice. 

The absence of an initial expansion in faujasite-type zeolite (Figure 5) is probably associated with the peculiarities of their structure and with the number and location of the cations. The heats of adsorption of water on zeolite NaX, in contrast with that of NaA, rapidly decrease in the... 

The ability of water molecules to promote a reaction depends on many factors. In most cases, zeolites with monovalent cations have low activity. However, the addition of water molecules to X and Y zeolites with monovalent ions increased the isomerization of cyclopropane (63). De-cationized zeolites can be promoted readily with water, and the process is reversible (2, 60, 64). It was shown (2) that the promoting ability of water molecules in faujasites is less when the Si02/Al203 increases. Dealu-minated faujasites are even more difficult to promote. For erionite and mordenite the maximum effect of water was observed only after treatment with liquid water and subsequent heating (2). The effect of water on zeolites saturated with polyvalent cations is less pronounced (65, 66, 67). However, the presence of multivalent cations stabilizes the catalytic activity. Water and alcohols were reported to promote ion exchanged zeolites for n-pentane isomerization (68) and n-hexadecane hydrocracking (69). 

Kasai and Jones (270) applied MAS to the study of water in zeolites A, X, Y, mordenite, ZSM-5, and silicalite. They found that although the signals were sometimes quite broad, their chemical shifts were characteristic of the zeolite (Fig. 59). They interpret this as the effect of the disruption of hydrogen bonding of bulk water by the zeolitic framework and of the interaction of water molecules with framework oxygens. An inverse relationship was found between the chemical shift and the Si/Al ratio. The chemical shift of water in silicalite is quite different from that in ZSM-5 and does not fit this... 

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