Crystalline sieving

Let us assume that the chemical transformations in zeolite catalyst systems occur vnthin the high surface area intracrystalline volumes. Then, for a reaction within a zeolite particle it is apparent that both the entry pores and the channel-cavity system must be open enough to allow transport of reactant molecules from the bulk phase to the active sites (and vice versa). Thus, any crystalline sieve that could sorb simple organic molecules such as w-hexane might conceivably have catalytic potential. Factors pertinent to these processes are discussed below. 

Zeolites (section C2.13) are unique because they have regular pores as part of their crystalline stmctures. The pores are so small (about 1 nm in diameter) that zeolites are molecular sieves, allowing small molecules to enter the pores, whereas larger ones are sieved out. The stmctures are built up of linked SiO and AlO tetrahedra that share O ions. The faujasites (zeolite X and zeolite Y) and ZSM-5 are important industrial catalysts. The stmcture of faujasite is represented in figure C2.7.11 and that of ZSM-5 in figure C2.7.12. The points of intersection of the lines represent Si or A1 ions oxygen is present at the centre of each line. This depiction emphasizes the zeolite framework stmcture and shows the presence of the intracrystalline pore stmcture. In the centre of the faujasite stmcture is an open space (supercage) with a diameter of about 1.2 nm. The pore stmcture is three dimensional. 

Flanigen E M, Bennet J M, Grose R W, Cohen J P, Patton R L, Kirchner R M and Smith J V 1978 Silicalite a new hydrophobic crystalline silica molecular sieve Nature 271 512-16... 

Gies FI, Marler B and Werthmann U 1998 Synthesis of porosils crystalline nanoporous silicas with cage- and channel-like void structures Moiecuiar Sieves Science and Technoiogy vo 1, ed FI G Karge and J Weitkamp (Berlin Springer) pp 35-64... 

Crystalline molecular sieve zeoHtes, and related molecular sieve materials that are not technically zeoHtes, eg, siHcaHte, AlPO s, SAPOs, etc. 

Typical pore size distributions for these adsorbents have been given (see Adsorption). Only molecular sieve carbons and crystalline molecular sieves have large pore volumes in pores smaller than 1 nm. Only the crystalline molecular sieves have monodisperse pore diameters because of the regularity of their crystalline stmctures (41). 

Moderately polar crystalline molecular sieves with low aluminum and low cation contents, siUca gel, activated alurnina, activated carbons with highly oxidh... 

Nonpolar sihcaUte, F-siUcahte, other high siUca content crystalline molecular sieves, activated carbons with reduced surfaces. 

Isotherms for H2O and / -hexane adsorption at room temperature and for O2 adsorption at Hquid oxygen temperature on 13X (NaX) zeoHte and on the crystalline Si02 molecular sieve siHcaHte are are shown in Figure 8 (43). SiHcaHte adsorbs water very weaMy. Further modification of siHcaHte by fluoride incorporation provides an extremely hydrophobic adsorbent, shown in Figure 9 (44). These examples illustrate the broad range of properties of crystalline molecular sieves. 

A significant advantage of adsorbents over other separative agents Hes in the fact that favorable equiHbrium-phase relations can be developed for particular separations adsorbents can be produced that are much more selective in their affinity for various substances than are any known solvents. This selectivity is particularly tme of the synthetic crystalline zeoHtes containing exchangeable cations. These zeoHtes became available in the early 1960s under the name of molecular sieves (qv) (9). 

A surprisiagly large number of important iadustrial-scale separations can be accompHshed with the relatively small number of zeoHtes that are commercially available. The discovery, characterization, and commercial availabiHty of new zeoHtes and molecular sieves are likely to multiply the number of potential solutions to separation problems. A wider variety of pore diameters, pore geometries, and hydrophobicity ia new zeoHtes and molecular sieves as weU as more precise control of composition and crystallinity ia existing zeoHtes will help to broaden the appHcations for adsorptive separations and likely lead to improvements ia separations that are currently ia commercial practice. 

AppHcations of soHd-state nmr include measuring degrees of crystallinity, estimates of domain sizes and compatibiHty in mixed systems from relaxation time studies in the rotating frame, preferred orientation in Hquid crystalline domains, as weU as the opportunity to characterize samples for which suitable solvents are not available. This method is a primary tool in the study of high polymers, zeoHtes (see Molecular sieves), and other insoluble materials. 

Adsorption. Although several types of microporous soHds are used as adsorbents for the separation of vapor or Hquid mixtures, the distribution of pore diameters does not enable separations based on the molecular-sieve effect. The most important molecular-sieve effects are shown by crystalline zeoHtes, which selectively adsorb or reject molecules based on differences in molecular size, shape, and other properties such as polarity. The sieve effect may be total or partial. 

Some commercially available molecular-sieve products and related materials are shown in Table 6, classified according to the basic 2eohte stmcture types. In most cases, the water content of the commercial product is below 1.5—2.5 wt % certain products, however, are sold as fully hydrated crystalline powders. 

Ion Exchange. Crystalline molecular sieve ion exchangers do not foUow the typical rules and patterns exhibited by organic and other inorganic ion exchangers. Many provide combinations of selectivity, capacity, and stability superior to the more common cation exchangers. Their commercial utilization has been based on these unique properties (59). 

Sodium alumiaate is widely used in the preparation of alumina-based catalysts. Aluminosilicate [1327-36-2] can be prepared by impregnating siHca gel with alumiaa obtained from sodium alumiaate and aluminum sulfate (41,42). Reaction of sodium alumiaate with siHca or siHcates has produced porous crystalline alumiaosiHcates which are useful as adsorbents and catalyst support materials, ie, molecular sieves (qv) (43,44). 

These tetrahedra are arranged in a number of ways to give the different zeohtes. The stmctures are unique in that they incorporate pores as part of the regular crystalline stmctures. The pores have dimensions of the order of molecular dimensions so that some molecules fit into the pores and some do not. Hence the zeohtes are molecular sieves (qv), and they are apphed in industrial separations processes to take advantage of this property. Some zeohtes and their pore dimensions are hsted in Table 2. 

There are numerous stmctures that are similar to 2eofites, such as aluminophosphate molecular sieves, AlPOs, but these have not found catalytic apphcations. Zeofites can be modified by incorporation of cations in the crystalline lattice which are not exchangeable ions, but can play catalytic roles. For example, sificahte, which has the stmcture of ZSM-5 but without Al, incorpora ting Ti in the lattice is a commercial catalyst for oxidation of phenol with H2O2 to give diphenols the catalytic sites may be isolated Ti cations (85). 

Adsorbents Table 16-3 classifies common adsorbents by structure type and water adsorption characteristics. Structured adsorbents take advantage of their crystalline structure (zeolites and sllicalite) and/or their molecular sieving properties. The hydrophobic (nonpolar surface) or hydrophihc (polar surface) character may vary depending on the competing adsorbate. A large number of zeolites have been identified, and these include both synthetic and naturally occurring (e.g., mordenite and chabazite) varieties. 

Type 3A sieves. A crystalline potassium aluminosilicate with a pore size of about 3 Angstroms. This type of molecular sieves is suitable for drying liquids such as acetone, acetonitrile, methanol, ethanol and 2-propanol, and drying gases such as acetylene, carbon dioxide, ammonia, propylene and butadiene. The material is supplied as beads or pellets. 

Type 13X sieves. A crystalline sodium aluminosilicate with a pore size of about 10 Angstroms which enables many branched-chain and cyclic compounds to be adsorbed, in addition to all the substances removed by type 5A sieves. 

The diffusion, location and interactions of guests in zeolite frameworks has been studied by in-situ Raman spectroscopy and Raman microscopy. For example, the location and orientation of crown ethers used as templates in the synthesis of faujasite polymorphs has been studied in the framework they helped to form [4.297]. Polarized Raman spectra of p-nitroaniline molecules adsorbed in the channels of AIPO4-5 molecular sieves revealed their physical state and orientation - molecules within the channels formed either a phase of head-to-tail chains similar to that in the solid crystalline substance, with a characteristic 0J3 band at 1282 cm , or a second phase, which is characterized by a similarly strong band around 1295 cm . This second phase consisted of weakly interacting molecules in a pseudo-quinonoid state similar to that of molten p-nitroaniline [4.298]. 

A major step in catalyst development was the introduction of crystalline zeolitic, or molecular sieve catalysts. Their activity is very high, some of the active sites being estimated at 10,000 times the effectiveness of amorphous silica-... 

Molecular sieves are an adsorbent that is produced by the dehydration of naturally occurring or synthetic zeolites (crystalline alkali-metal aluminosilicates). The dehydration leaves inter-crystalline cavities into which normal paraffin molecules are selectively retained and other molecules are excluded. This process is used to remove normal paraffins from gasoline fuels for improved combustion. Molecular sieves are used to manufacture high-purity solvents. 

The molecular sieve process uses synthetically manufactured. solid crystalline zeolite in a dry bed to remove gas impurities. The crystalline... 

A mixture of 40.5 g (0.15 mol) of 3-carbethoxy-4-hydroxy-2-methyl-2H-1.2-benzothiazine 1,1 -dioxide, 20.6 g (0.21 mol) of 3-amino-5-methylisoxazole, and 2,500 ml of xylene was refluxed for 24 hours in a Soxhiet apparatus, the thimble of which contained 60 g of Linde type 4A molecular sieve. The mixture was cooled to 25°C and the resulting crystalline precipitate was collected and washed with ether to give 44 g of crude product. Recrystallization from 1,6(X) ml of 1,4-dioxan gave 34.7 g of material, MP 265°C to 271°C dec. 

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