Rapid syntheses, zeolites

In conclusion, the rapid crystallization method is very effective not only for rapid synthesis, but also for synthesis of metal-containing uniform zeolitic materials which show higher catalytic activity and selectivity. 

The seeding can be performed under vacuum [102] or by electrophoretic deposition in aqueous or non-aqueous medium [103]. The latter method has been applied to the rapid synthesis of A-type zeolite membranes. Two strategies can be used for an electrostatic attachment of the seeds to the support either a fine-tuned surface charge by pH control and measurement of the support zeta-potential or the adsorption of positively charged polymers [104], and immersion in a suspension whose pH is such that the seed particles are negatively... 

Sebastian V, Mallada R, Coronas J, Julbe A, Terpstta RA, Dirrix RWJ. MW-assisted hydrothermal rapid synthesis of capillary MFI-type zeolite-ceramic membranes for pervaporation application. J Membr Sci 2010 355 28-35. 

Kang Z, Zhang X, Liu H, Qiu J, Yeung KL. A rapid synthesis route for Sn-beta zeolites by steam-assisted conversion and their catalyhc performance in Baeyer-Vhliger oxidation. Chem Eng J 2013 218 425-32. 

Shingare and co-workers have presented for the first time a successful implementation of ultrasound irradiation for the rapid synthesis of a-hydroxy phosphonates (521) and a-amino phosphonates (525) under solvent-free conditions from triethyl phosphite (524), aromatic aldehydes (523) and amines (522) using camphor sulfonic acid (CSA) (Scheme 130). One-pot, three-component Kabachnik-Fields synthesis of a-aminophos-phonates (529) from carbonyl compounds (526), primary amines (527), and dibenzyl/dimethyl/diethyl substituted phosphites (528) has been carried out in high yields, using H-beta zeolite as a reusable catalyst (Scheme 131). Zhang and co-workers have developed the nickel-catalysed Arbuzov type phosphonylation to afford phenyl substituted phosphonates (532) in the reaction of aryl triflates (530) with triethyl phosphite (531), in which KBr, as an additive, promoted the Sn2 catalytic step (Scheme 132). ... 

Zeolite-Based All lation. Zeohtes have the obvious advantages of being noncorrosive and environmentally benign. They have been extensively researched as catalysts for ethylbenzene synthesis. Eadier efforts were unsuccessful because the catalysts did not have sufficient selectivity and activity and were susceptible to rapid coke formation and deactivation. 

Our group has recently observed (ref. 10) that often synthesis time of zeolites can be substantially shortened when microwave radiation is applied instead of conventional heating. Table 3 gives some examples. Also a narrow crystal size distribution is obtained in this way. The crystallization temperature is rapidly (1 min) reached by microwave heating, this may be a factor in homogeneous and essentially simultaneous nucleation. 

The most successful application of microwave energy in the preparation of heterogeneous solid catalysts has been the microwave synthesis and modification of zeolites [21, 22], For example, cracking catalysts in the form of uniformly sized Y zeolite crystallites were prepared by microwave irradiation in 10 min, whereas 10-50 h were required by conventional heating techniques. Similarly, ZSM-5 was synthesized in 30 min by use of this technique. The rapid internal heating induced by microwaves not only led to a shorter synthesis time, and high crystallinity, but also enhanced substitution and ion exchange [22]. 

The name of zeolites, which originates from the Greek words zeo (to boil) and lithos (stone), was given some 250 years ago to a family of minerals (hydrated aluminosilicates) that exhibited intumescence when heated in a flame. However, the history of zeolites really began 60 years ago with the development of synthesis methods. Commercial applications in three main fields—ion exchange, adsorption, and catalysis—were rapidly developed, the corresponding processes being more environmentally friendly than their predecessors. 

Microwave Synthesis of Zeolites and Molecular Sieves The use of microwaves holds promise for efficiency improvements in zeolite synthesis due to the rapid heating possible when using microwave radiation [166], The first report of microwave synthesis of zeolites was by Mobil Oil in 1988, which broadly claimed the synthesis of zeolite materials in the presence of a microwave-sympathetic material, such as water or other pro tic component [167]. A number of reports have appeared since, including synthesis of zeolites Y, ZSM-5 [168] and metaUoaluminophosphate-type materials, such as MAPO-5 [169], There have also been extensive investigations in using microwaves for zeoHte membrane synthesis. Recent reviews discuss the progress in microwave zeoHte synthesis [170, 171]. 

I. Hasegawa and S. Sakka, Silicate Species with Cagelike Structure in Solutions and Rapid Solidification with Organic Quaternary Ammonium Ions, Zeolite Synthesis (ACS Symposium Series 398) Am, Chem. Soc., Washington, DC 1989, p.140/51... 

The most important factor in zeolite synthesis in the laboratory, or factory, is the rate of crystallization. Composition and concentration of the liquid solution acting on the solids is important to the process as is the absolute necessity of maximum disorder of the Si-O-Al bonds in the initial solids reacted (Zhdanov, 1970). It is thus evident that not only bulk chemical (equilibrium) factors are important in the initial crystallization of zeolites but also the. relative free energies of the reactants. It is apparent that zeolite equilibria are essentially aqueous i.e., that silicate equilibrium or approach to it is attained through reaction with solutions, and thus the solubilities of the solids present are of primary importance. If materials are slow to enter into solution they are essentially bypassed in the rapid crystallization sequence (Schwochow and Heinze, 1970 Aiello, et al , 1970). In most studies the zeolites precipitated from solution appear to respond to the laws concerning chemical activity of solutions (Zhdanov, 1970). 

Synthesis of Zeolite X. Zeolite X was crystallized from a batch of overall composition 4 Na20-Al203-5 SiO2-200 H20 at 90° C (8). The crystallization curve is shown in Figure 7. After an induction period of 2.4 hours, zeolite X was formed rapidly as a single phase at a conversion... 

A widely studied example of this kind is the synthesis of methyl isobutyl ketone (MIBK, used as a solvent for inks and lacquers) from acetone. The former was previously prepared from the latter through a catalytic three-step process base-catalysed production of 4-hydroxy-4-methylpentan-2-one, acid dehydration into mesityloxide (MO), then hydrogenation of MO on a Pd catalyst. Since acetone aldolization occurs through acid catalysis as shown over a H-MFI zeolite at 433 K (MO is the main reaction product, the aldolization product being rapidly dehy-drated[5]), it is possible, by associating with the acid catalyst a hydrogenation phase,... 

MF1 type zeolites are known to show enhanced selectivity to p-substituted products in alkylation and isomerization of aromatic molecules [e.g. 1,2,3,4]. This shape selectivity is more pronounced with larger zeolite crystals and can be further enhanced by modification of the parent zeolites through post-synthesis treatments like impregnation with basic oxides, metal salts or the deposition of silica or coke [3,5,6,7]. The gain in selectivity is, however, usually accompanied with loss in catalytic activity and in some cases more rapid deactivation [8,9]. Despite the large number of patents and reports in open literature, the reasons for the enhancement of shape selectivity of MFI zeolites by post-synthesis treatment and the limits of the severity of this treatment are not unequivocally explained to date. 

Second, the amount of all small silicates present in solution seems to be constant throughout the duration of the synthesis. This finding is in line with the fast mutual exchange observed in silicate solutions (vide supra). Moreover, it indicates that if the zeolite is indeed grown from dissolved small silicates, the equilibrium between the polymeric and the smaller silicates is rapid enough to keep the amount of smaller silicates in solution at a constant level. The zeolite formation stops when the solution is no longer supersaturated with silica, which in this case means after about 10 days (see Table I). 

Mechanism of Rapid Zeolite Crystallizations and Its Applications to Catalyst Synthesis... 

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