Acid zeolites

Despite the enormous commercial success and widespread use of acidic zeolite catalysts, important questions on the local structure of zeolitic materials remain unanswered. The local structure of aluminum in the zeolites has proven rather elusive to investigation. 

Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) also had some success in determining proton positions. Side-band analysis from solid-state H NMR was used to determine proton positions [19, 20] in ZSM-5 type zeolites. 

Weaker bases such as toluene or isopropanol induced some relaxation of the aluminum in acidic zeolites. Water also exhibited a similar effect [32], R.W. Joyner, 

One of the disadvantages of EXAFS in general is that it is an averaging technique. Thus it is very important to make sure the zeolites are very well defined. Other techniques such as Al MAS NMR spectroscopy and in situ infrared spectroscopy are needed to ensure single aluminum sites. Depending on the data quality it is also possible to define more than one type of site however, in this case 

However, the accuracy of the ah initio calculations for the large number of multiple scattering pathways present in the XANES region is limited and thus difficulties arise in the interpretation of the data (see above). 

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A new dimension to acid-base systems has been developed with the use of zeolites. As illustrated in Fig. XVIII-21, the alumino-silicate faujasite has an open structure of interconnected cavities. By exchanging for alkali metal (or NH4 and then driving off ammonia), acid zeolites can be obtained whose acidity is comparable to that of sulfuric acid and having excellent catalytic properties (see Section XVIII-9D). Using spectral shifts, zeolites can be put on a relative acidity scale [195]. An important added feature is that the size of the channels and cavities, which can be controlled, gives selectivity in that only... 

To explain how solid acids such as Nafion-H or HZSM-5 can show remarkable catalytic activity in hydrocarbon transformations, the nature of activation at the acidie sites of such solid acids must be eon-sidered. Nafion-H contains acidic -SO3H groups in clustered pockets. In the acidic zeolite H-ZSM-5 the active Bronsted and Tewis acid sites are in close proximity (—2.5 A). 

A solution of trifluoroacetic acid in toluene was found to be advantageous for cydization of pyruvate hydrazoncs having nitro substituents[4]. p-Toluene-sulfonic acid or Amberlyst-15 in toluene has also been found to give excellent results in preparation of indole-2-carboxylale esters from pyruvate hydra-zoiies[5,6J. Acidic zeolite catalysts have been used with xylene as a solvent to convert phenylhydraziiies and ketones to indoles both in one-flask procedures and in a flow-through reactor[7]. 

The use of zeolites is particularly advantageous for self-Diels-Alder reactions of gaseous dienes because it reduces the polymerization of the reactant. An example is the cyclodimerization of 1,3-butadiene to 4-vinylcyclohexene [20a] carried out at 250 °C with satisfactory conversion when non-acidic zeolites, such as large-pore zeolites Na-ZSM-20, Na- S and Na-Y, are used. 

Figure 4.19 DKR of sec-alcohols catalyzed by acid zeolites and a lipase.

Jacobs et al. employed an acidic zeolite catalyst for the racemization of sec-alcohols, which occurs through the formation of carbocations [44] (Figure 4.19). The KR is catalyzed by CALB in the presence of vinyl octanoate as acyl donor. DKR takes place successfully in a biphasic system (octane/H2O, 1 1) at 60 °C. 

The Ag-silica-alumina material is furthermore suited to assist in sterically hindered aromatic brominations. As an example we converted 1,3,5-tri-t-butylbenzene into 2,4,6-tri-t-butylbromobenzene. When using an acidic zeolite and Br2 de-alkylation prevails and 3,5-di-t-butylbromobenzene is formed (ref. 29). 

The probe reaction utilized a 1/1 molar mixture of methanol and isobutanol over H-mordenite, a strongly acidic zeolite comprised of linear one-dimensional channels made up of 12-ring 6.5 by 7.0 A windows [8]. There is a side-pocket system in H-... 

It is well known also that higher alkanes suffer radical gas phase oxidation above 723 K. Therefore, their use requires catalysts active and selective for deNOx at lower temperatures. The mechanism of NOx elimination is still debated a redox mechanism involving Cu ions is probable, and isolated Cu cations exchanged into MFI [4,5] or mordenite [6] have been found to be more active than CuO clusters. It must be emphasized, however, that acid zeolites exhibit good activity at high temperature, and acid mechanisms have been proposed [7-10]. In presence of Cu this acid mechanism disappears probably due to the decrease of the acidity of mordenite upon Cu exchange [6]. According to... 

Traditionally, the production of LABs has been practiced commercially using either Lewis acid catalysts, or liquid hydrofluoric acid (HF).2 The HF catalysis typically gives 2-phenylalkane selectivities of only 17-18%. More recently, UOP/CEPSA have announced the DetalR process for LAB production that is reported to employ a solid acid catalyst.3 Within the same time frame, a number of papers and patents have been published describing LAB synthesis using a range of solid acid (sterically constrained) catalysts, including acidic clays,4 sulfated oxides,5 plus a variety of acidic zeolite structures.6"9 Many of these solid acids provide improved 2-phenylalkane selectivities. 

The use of an enzyme in a cascade using nanoencapsulation has also been demonstrated [23]. In this case, the dynamic kinetic resolution (DKR) of secondary alcohols was achieved with an acidic zeolite and an incompatible enzyme, Candida antarctica lipase B (CALB) (Scheme 5.8). 

Scheme 5.8 DKR of a secondary alcohol using an acidic zeolite racemization catalyst in conjunction with CALB. The zeolite was encapsulated using an Lb L method in order to overcome the incompatibility of the two catalysts.

DKR of secondary alcohols with acidic zeolite (for racemization) and enzyme (CALB) (for esterification) LbL deposition onto zeolite itself... 

Formation of products in paraffin cracking reactions over acidic zeolites can proceed via both unimolecular and bimolecular pathways [4], Based on the analysis of the kinetic rate equations it was suggested that the intrinsic acidity shows better correlation with the intrinsic rate constant (kinl) of the unimolecular hexane cracking than with the apparent rate constant (kapp= k K, where K is the constant of adsorption equilibrium). In... 

The highly oxygenated bio oil can be de-oxygenated, and thereby upgraded, over acidic zeolite catalysts through the formation of mainly water at low temperatures and C02 and CO at higher temperatures [1-3], Successful catalytic pyrolysis of woody biomass over Beta zeolites has been performed in a fluidized bed reactor in [4]. A drawback in the use of pure zeolitic materials has been the mechanical strength of the pelletized zeolite particles in the fluidized bed. 

Alkylation of benzene with propylene was carried out with the acid zeolites, pelletized, crushed, and sieved at 0.25-0.42 mm diameter. The reaction was performed in an automated high pressure stainless steel reactor, at 3.5 MPa, temperatures ranging from 125 to 200°C, WF1SV from 12 to 18 h"1 referred to the olefin, and benzene to propylene (B/P) molar ratio of 3.5. More details can be found in [7]. 

Synergism of acidic zeolite and Pt/zeolite in aromatics transalkylation... 

Whereas over the dual-bed catalyst system, namely Pt/Z12(80) HB(20), a significant improvement in benzene purity up to 94.60% was observed. This is ascribed due to selective cracking of naphthenes over acidic zeolite H-Beta at the bottom bed. 

SCHEME 1. Acid-zeolite catalyzed formation of alkyl glucosides by Fischer glucosylation and by transacetalation of butyl glucosides. 

Scheme 2. Fischer glycosylation of GalNAc catalyzed by acid zeolites.

Bhaskar and Loganathan96 described O-peracetylation of monosaccharides, disaccharides, and methyl glycosides (94) with acetic anhydride under catalysis by acid zeolites. From the panel of zeolites tested (HY, HEMT, HZSM-5, HZSM-12, HZSM-22, and H-beta), the large-pore zeolite H-beta provided the best yields of the fully acetylated sugars, most of them being over 85% and up to 99%, with the pyranose forms 95 accounting for 66-100% of the reaction products (Scheme 22). 

Subsequently, Goncalves cl al.97 reported the acetylation of glycerol with acetic acid performed over different solid acids, including montmorillonite K-10 and such acid zeolites as HZSM-5 and HUSY. Among the siliceous porous materials examined, montmorillonite K-10 gave the best performance, with 96% conversion into the mono-, di- and tri-acetylated derivatives. When zeolites were used, the conversion was lower than with the other catalysts, giving a 30% conversion for HZSM-5 and only 14% for HUSY. However, selectivity for the primary monoacetylated product,... 

Scheme 24. Selective deprotection of sugar di-O-isopropylidene acetals using acid zeolites.

Selective removal of one isopropylidene group from a diacetal may be achieved by a variety of procedures, most of them involving protic or Lewis acids.100 Particularly common is the hydrolysis of the acetal engaging of the primary position of di-O-isopropylidene derivatives. Bhaskar et al,101 studied the selective deprotection of di-O-isopropylidene acetals derived from D-glucose, D-xylose, and D-mannose, using acid zeolites and montmorillonite K-10. When 102 was submitted to acid hydrolysis in aqueous methanol, the best yields (85—96%) for the monoacetal 105 were obtained when H-beta and HZSM-5 zeolites were employed as catalysts (Scheme 24, Table IV). HY zeolite proved to be ineffective, whereas the yield obtained for the montmorillonite K-10-catalyzed reaction was low (22%). The zeolites found most effective were then used for the hydrolysis of the diacetal 103 and 104, providing excellent yields for the desired corresponding monoacetals 106 and 107. 

E. Baburek and J. Novakova, Isomerization of n-butane over acid zeolites, role of Brpnsted and Lewis acid sites, Appl. Catal. A Gen., 185 (1999) 123-130. 

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