Zeolitic diffusion

Karge HG, Karger J (2008) Application of IR Spectroscopy, IR Microscopy and Optical Interference Microscopy on Diffusion Zeolites... 

Vibrational Spectroscopy. Infrared absorption spectra may be obtained using convention IR or FTIR instrumentation the catalyst may be present as a compressed disk, allowing transmission spectroscopy. If the surface area is high, there can be enough chemisorbed species for their spectra to be recorded. This approach is widely used to follow actual catalyzed reactions see, for example. Refs. 26 (metal oxide catalysts) and 27 (zeolitic catalysts). Diffuse reflectance infrared reflection spectroscopy (DRIFT S) may be used on films [e.g.. Ref. 28—Si02 films on Mo(llO)]. Laser Raman spectroscopy (e.g.. Refs. 29, 30) and infrared emission spectroscopy may give greater detail [31]. 

The ortho- and meto-isomers are bulkier than the para-iaomer and diffuse less readily in the zeolite pores. The transport restriction favours their conversion into the /lara-isomer, which is fonned in excess of the equilibrium concentration. Because the selectivity is transport influenced, it is dependent on the path length for transport, which is the length of the zeolite crystallites. 

Figure C2.7.13. Schematic representation of diffusion and reaction in pores of HZSM-5 zeolite-catalysed toluene disproportionation the numbers are approximate relative diffusion coefficients in the pores 1131.

Karge and Rutbveu, Diffusion in Zeolites and Qthei Miciopoious Solids, Wiley, New York, 1992. 

Numerical values for solid diffusivities D,j in adsorbents are sparse and disperse. Moreover, they may be strongly dependent on the adsorbed phase concentration of solute. Hence, locally conducted experiments and interpretation must be used to a great extent. Summaries of available data for surface diffusivities in activated carbon and other adsorbent materials and for micropore diffusivities in zeolites are given in Ruthven, Yang, Suzuki, and Karger and Ruthven (gen. refs.). 

The effect of temperature on diffusivities in zeolite ciystals can be expressed in terms of the Eyring equation (see Ruthven, gen. refs.). 

The more permeable component is called the. st ga.s, so it is the one enriched in the permeate stream. Permeability through polymers is the product of solubihty and diffusivity. The diffusivity of a gas in a membrane is inversely proportional to its kinetic diameter, a value determined from zeolite cage exclusion data (see Table 22-23 after Breck, Zeolite Molecular Sieves, Wiley, NY, 1974, p. 636). 

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]. 

The higher selectivity of zeolites is attrihuted to its smaller pores, which allow diffusion of only smaller molecules through their pores, and... 

The important property of ZSM-5 and similar zeolites is the intercrystalline catalyst sites, which allow one type of reactant molecule to diffuse, while denying diffusion to others. This property, which is based on the shape and size of the reactant molecules as well as the pore sizes of the catalyst, is called shape selectivity. Chen and Garwood document investigations regarding the various aspects of ZSM-5 shape selectivity in relation to its intercrystalline and pore structure. 

Active matrix contributes significantly to the overall performance of the FCC catalyst. The zeolite pores are not suitable for cracking of large hydrocarbon molecules generally having an end point > d00 [-(482°C) they are too small to allow diffusion of the large molecules to the cracking sites. An effective matrix must have a porous structure to allow diffusion of hydrocarbons into and out of the catalyst. 

Sorption, Diffusion, and Catalytic Reaction in Zeolites L. Riekert... 

FIGURE 13.38 The structure of the ZSM-5 zeolite catalyst. Reactants diffuse through the channels, which are narrow enough to hold intermediates in positions favorable for reaction. 

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

In order to design a zeoHte membrane-based process a good model description of the multicomponent mass transport properties is required. Moreover, this will reduce the amount of practical work required in the development of zeolite membranes and MRs. Concerning intracrystaUine mass transport, a decent continuum approach is available within a Maxwell-Stefan framework for mass transport [98-100]. The well-defined geometry of zeoHtes, however, gives rise to microscopic effects, like specific adsorption sites and nonisotropic diffusion, which become manifested at the macroscale. It remains challenging to incorporate these microscopic effects into a generalized model and to obtain an accurate multicomponent prediction of a real membrane. 

Since their development in 1974 ZSM-5 zeolites have had considerable commercial success. ZSM-5 has a 10-membered ring-pore aperture of 0.55 nm (hence the 5 in ZSM-5), which is an ideal dimension for carrying out selective transformations on small aromatic substrates. Being the feedstock for PET, / -xylene is the most useful of the xylene isomers. The Bronsted acid form of ZSM-5, H-ZSM-5, is used to produce p-xylene selectively through toluene alkylation with methanol, xylene isomerization and toluene disproportionation (Figure 4.4). This is an example of a product selective reaction in which the reactant (toluene) is small enough to enter the pore but some of the initial products formed (o and w-xylene) are too large to diffuse rapidly out of the pore. /7-Xylene can, however. 

The stability of catalyst is one of the most important criteria to evaluate its quality. The influence of time on stream on the conversion of n-heptane at SSO C is shown in Fig. 5. The conversion of n-heptane decreases faster on HYl than on FIYs with time, so the question is Could the formation of coke on the catalyst inhibit diffusion of reactant into the caves and pores of zeolite and decrease the conversion According to Hollander [8], coke was mainly formed at the beginning of the reaction, and the reaction time did not affect the yield of coke. Hence, this decrease might be caused by some impurities introduced during the catalyst synthesis. These impurities could be sintered and cover active sites to make the conversion of n-heptane on HYl decrease faster. 

There exist a number of other methods for the separation of diamondoids from petroleum fluids or natural gas streams (1) a gradient thermal diffusion process [54] is proposed for separation of diamondoids (2) a number of extraction and absorption methods [53,83] have been recommended for removing diamondoid compounds from natural gas streams and (3) separation of certain diamondoids from petroleum fluids has been achieved using zeolites [56, 84] and a number of other solid adsorbents. 

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