Molecular sieves applications

Molecular sieves are synthetic zeolites that can be manufactured with extremely close control of pore size. Therefore, they can be tailored to suit specific applications. In addition to gas drying applications, molecular sieves are used for the separation of gases and vapors on the basis of molecular size and shape. Surface areas range from 350 to 1000 ft2/ft3. 

During their technical application, molecular sieve catalysts are generally used under the conditions of multicomponent adsorption and diffusion. Selective measurement of the diffusivity of individual components is therefore of both theoretical and practical relevance. The traditional way to perform... 

Casci J L 1994 The preparation and potential applications of ultra-large pore molecular sieves a review Stud. Surf. Sc/. Catai. 85 329-56... 

Martens J A and Jacobs P A 1999 Phosphate-based zeolites and molecular sieves Catalysis and Zeolites, Fundamentals and Applications ed J Weitkamp and L Puppe (Berlin Springer) pp 53-80... 

Ammonium Ion Removal. A fixed-bed molecular-sieve ion-exchange process has been commercialized for the removal of ammonium ions from secondary wastewater treatment effluents. This application takes advantage of the superior selectivity of molecular-sieve ion exchangers for ammonium ions. The first plants employed clinoptilolite as a potentially low cost material because of its availability in natural deposits. The bed is regenerated with a lime-salt solution that can be reused after the ammonia is removed by pH adjustment and air stripping. The ammonia is subsequentiy removed from the air stream by acid scmbbing. 

Using 2eohte catalysts, the NO reduction takes place inside a molecular sieve ceramic body rather than on the surface of a metallic catalyst (see Molecularsieves). This difference is reported to reduce the effect of particulates, soot, SO2/SO2 conversions, heavy metals, etc, which poison, plug, and mask metal catalysts. ZeoHtes have been in use in Europe since the mid-1980s and there are approximately 100 installations on stream. Process applications range from use of natural gas to coal as fuel. Typically, nitrogen oxide levels are reduced 80 to 90% (37). 

The main applications of molecular sieves to purification comprise ... 

The general purification methods listed for xylene are applicable. p-Xylene can readily be separated from its isomers by crystn from such solvents as MeOH, EtOH, isopropanol, acetone, butanone, toluene, pentane or pentene. It can be further purified by fractional crystn by partial freezing, and stored over sodium wire or molecular sieves Linde type 4A. [Stokes and French J Chem Soc, Faraday Trans 1 76 537 1980.]... 

The structural complexity of the 3D framework aluminosilicates precludes a detailed treatment here, but many of the minerals are of paramount importance. The group includes the feldspars (which are the most abundant of all minerals, and comprise 60% of the earth s crust), the zeolites (which find major applications as molecular sieves, desiccants, ion exchangers and water softeners), and the ultramarines which, as their name implies, often have an intense blue colour. All are constructed from Si04 units in which each O atom is shared by 2 tetrahedra (as in the various forms of Si02 itself), but up to one-half of the Si... 

A rather unexpected discovery was made in connection to these investigations [49]. When the 1,3-dipolar cycloaddition reaction of la with 19b mediated by catalyst 20 (X=I) was performed in the absence of MS 4 A a remarkable reversal of enantioselectivity was observed as the opposite enantiomer of ench-21 was obtained (Table 6.1, entries 1 and 2). This had not been observed for enantioselective catalytic reactions before and the role of molecular sieves cannot simply be ascribed to the removal of water by the MS, since the application of MS 4 A that were presaturated with water, also induced the reversal of enantioselectivity (Table 6.1, entries 3 and 4). Recently, Desimoni et al. also found that in addition to the presence of MS in the MgX2-Ph-BOX-catalyzed 1,3-dipolar addition shown in Scheme 6.17, the counter-ion for the magnesium catalyst also strongly affect the absolute stereoselectivity of the reac-... 

Separation of isomers is an application where zeolite membranes could be specifically interesting because of their well-defined pores that lead to molecular sieving effects. An application that is often considered is the xylene isomerization and related reactions. 

Kokufuta, E Jinbo, E, A Hydrogel Capable of Facilitating Polymer Diffusion through the Gel Porosity and Its Application in Enzyme Immobilization, Macromolecules 25, 3549, 1992. Kresge, CT Leonowicz, ME Roth, WJ Vartuli, JC Beck, JS, Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism, Nature 359, 710, 1992. 

Tietz, D Gottheb, MH Eawcett, JS Chrambach, A, Elechophoresis on Uncrosslinked Polyacrylamide Molecular Sieving and Its Potential Applications, Elechophoresis 7, 217, 1986. 

Volume 158 Molecular Sieves From Basic Research to Industrial Applications... 

Methane can be oxidatively coupled to ethylene with very high yield using the novel gas recycle electrocatalytic or catalytic reactor separator. The ethylene yield is up to 85% for batch operation and up to 50% for continuous flow operation. These promising results, which stem from the novel reactor design and from the adsorptive properties of the molecular sieve material, can be rationalized in terms of a simple macroscopic kinetic model. Such simplified models may be useful for scale up purposes. For practical applications it would be desirable to reduce the recycle ratio p to lower values (e.g. 5-8). This requires a single-pass C2 yield of the order of 15-20%. The Sr-doped La203... 

A similar series of reactions was performed by Paulsen and Hdlck141 for the preparation of the T-antigenic, unprotected, amino acid-disaccha-rides 200 and 201, starting from the 4,6-0-benzylidene-N-(benzyloxy-carbonyl) benzyl esters 198 and 199, respectively, by condensation with 110 in the presence of mercury dicyanide-mercury dichloride and molecular sieves 4A, and deprotection of the product. Sinay and co-workers148 also reported the synthesis of hexa-O-acetyl derivatives of 200 and 201 by application of the sequence of azido-nitration-bromination. 

Bidentate ligands with very wide bite angles (like dpephos or xantphos, Scheme 4) are likely to form unstable chelates prone to dechelation at elevated temperatures, thus giving another route to monophosphine species. The application of such ligands to the crosscoupling of sterically hindered bromides and arylboronic acids under strictly anhydrous conditions enforced by the addition of molecular sieves has been shown to be advantageous (118).398... 

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