Adsorbents silicalite

Figures 5 and 6, respectively, show the isosteric heats of adsorption of pure CO2 and C2H6 as functions of adsorbate loadings (surface excess) on three different microporous adsorbents (silicalite crystals, NaX zeolite crystals, and granular BPL activated carbon). Figure 7 shows similar plots for adsorption of three different pure gases (CH4, SFf, and CO2) on NaX zeolite crystals and pellets. The data for adsorption of CO2 and C2H6 on BPL carbon and those for adsorption of CH4 on NaX zeolite pellets were calculated with Eq. (11) using the pure gas adsorption isotherms at different temperatures [22]. The CH4 isotherms on the zeolite pellets were measured in our laboratory. All other data were measured by using a Tian-Calvet type of calorimeter [19,20].

Role of the organic feed XRD powder patterns and FT-IR spectra confirmed that pure MFI-type Ti-silicalite (TS-1) was obtained [18-23], with a surface area of 530 m g". FT-IR spectra of adsorbed pyridine (Fig. 39.2) showed the presence only of weak Bronsted and Lewis sites [24,25], as confirmed by the complete evacuation from the surface at 373 K. 

Adsorbents Table 16-3 classifies common adsorbents by structure type and water adsorption characteristics. Structured adsorbents take advantage of their crystalline structure (zeolites and silicalite) and/or their molecular sieving properties. The hydrophobic (nonpolar surface) or hydrophilic (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. 

Conclusions, some of them contrary to the above, were reached more recently by Zhuang et al. (145) from a combination of 31P and 1H MAS NMR spectroscopy of adsorbed trimethylphosphine. These authors found not only Lewis acid sites (vide infra), but also Brpnsted acid sites in TS-1 (145). They claimed that the 1H, 29Si MAS NMR spectra and the resonance related to Brpnsted acid sites in the 31P MAS NMR demonstrated clearly that the presence of Ti in the framework results in the formation of a new OH group, titanols, which is more acidic than the silanols of silicalite-1 (145) . The peak at 4.3 ppm in the 31P MAS NMR spectra was assigned to a ((CH3)3P-H)+ complex arising from the interaction of (CH3)3P with Brpnsted acid sites present on TS-1. The origin of this proton is not clear at present, especially because the MAS NMR spectra of the same TS-1 samples did not differ significantly from those of silicalite-1 (145) the latter, when free from impurities, is not known to be a Brpnsted acid. 

Bolis et al (43) reported volumetric data characterizing NH3 adsorption on TS-1 that demonstrate that the number of NH3 molecules adsorbed per Ti atom under saturation conditions was close to two, suggesting that virtually all Ti atoms are involved in the adsorption and have completed a 6-fold coordination Ti(NH3)204. The reduction of the tetrahedral symmetry of Ti4+ ions in the silicalite framework upon adsorption of NH3 or H20 is also documented by a blue shift of the Ti-sensitive stretching band at 960 cm-1 (43,45,134), by a decrease of the intensity of the XANES pre-edge peak at 4967 eV (41,43,134), and by the extinction of the resonance Raman enhancement of the 1125 cm-1 band in UV-Raman spectra (39,41). As an example, spectra in Figs. 15 and 16 show the effect of adsorbed water on the UV-visible (Fig. 15), XANES (Fig. 16a), and UV-Raman (Fig. 16b) spectra of TS-1. 

The direct conversion of propene to its epoxide, in near quantitative yields, with aqueous H202 will be environmentally more benign. One of the unique features of TS-1 as a solid oxidation catalyst is its ability to utilize aqueous H202 as the oxidant for such conversions. This ability of TS-1 derives from the fact that silicalite-1 is hydrophobic, in contrast to the hydrophilic amorphous Ti-Si02. Consequently, hydrophobic reactants, such as alkenes, are preferentially adsorbed by TS-1, thus precluding the strong inhibition by H20 observed with amorphous Ti-Si02. 

Kulprathipanja, S. and Neuzil, R.W. (1983) Process for separabng normal paraffins using silicalite adsorbent. U.S. Patent 4,367,364. 

Examples of rate-selective adsorption are demonstrated using silicalite adsorbent for separation of Ciq-Cm n-paraffins from non- -paraffins [40, 41] and Ciq-Ch mono-methyl-paraffins from non-n-paraffins [42-45]. Silicalite is a ten-ringed zeolite with a pore opening of 5.4A x 5.7 A [22]. In the case of -paraffins/non-n-paraffins separation [40, 41], n-paraffins enter the pores of silicalite freely, but non-n-paraffins such as aromatics, naphthenes and iso-paraffins diffuse into the pores more slowly. However, the diffusion rates of both normal -paraffins and non-n-paraffins increase with temperature. So, one would expect to see minimal separation of n-paraffins from non-n-paraffins at high temperatures but high separation at lower temperature. 

Another example of rate-selective adsorption is the separahon of diisopropylbenzene isomers using a silicalite adsorbent. Figure 6.12 shows the adsorption rates of 1,3-diispropylbenzene and 1.4-di-isopropylbenzene into silicalite adsorbent. In particular, it illustrates the more rapid adsorption of 1,4-di-isopropylbenzene compared to 1,3-di-isopropylbenzene. 

Figure 6.12 Rate-selective adsorption of diisopropylbenzene isomers on Silicalite adsorbent.

In addition, the infrared examination of the mechanism of propane and oxygen interaction with the sample (Fig. 6) indicates the different mechanism of interaction of the intermediate propylene as compared to other supported vanadium catalysts such as V-Ti02 (10). In particular, the formation of a 7t-bonded complex stabilized by a nearlying silanol with weak basic character due to the inductive effect of vicinal vanadium is shown. This indicates the relative inertness of the V sites in the silicalite towards 0-insertion or allylic H-abstraction on the adsorbed propylene. It is evident that the reduced reactivity of V sites in these reactions limits the consecutive reactions of intermediate propylene, thus enhancing the selectivity in the formation of this product. 

In contrast, an extremely low activity was observed for the gallium-modified silicalite-1. scrambling started first at 723 K, which clearly indicates that Bronsted acid sites are necessary to activate propane adsorbed on zeolites Ga/ HZSM-5 179,181. A low activity was also observed for C-2-propane adsorbed on zeolite HZSM-5 in the absence of gallium. On this catalyst, C scrambling was observed after heating at 573 K for 20 min, and the theoretical 2 1 ratio of the signal intensities of methyl and methylene groups was reached after 80 min at 573 K. 

Nicholas et al. (67) have performed MD calculations of propane in sili-calite in which the propane molecule is given complete flexibility. The calculations, which have been detailed previously for methane diffusion, employed a large simulation box with multiple sets of adsorbates to ensure good statistics. The framework was kept fixed and data were collected over a 40-ps run. The results predict diffusion coefficients in very good agreement with the values of Caro et al. (71). The calculated values for a concentration of 4 and 12 propane molecules per silicalite unit cell are 0.12 and 0.005 X 10 8 m2/s, respectively. These values for propane are far lower than those of Nowak et al. (63), the reason for this is that Nicholas et al. used flexible adsorbate molecules, whereas Nowak et al. used rigid ones. 

The efficiency of the CB-MC technique has been used by Maginn et al. (769), who considered the low-occupancy thermodynamics of sorption of alkanes as long as C25 in silicalite. The locations of such long molecules are no longer correctly predicted by considering the end-to-end vector and the chain midpoint. To overcome this problem, a coarse-graining technique was used to describe both the adsorbate and the zeolite, allowing for accurate microscopic characterization. 

Sorption energies in silicalite were found to be spread over a relatively small range, 18 and 9 kJ/mol, for full- and reduced-charge models, respectively. In each case, the preferential binding order was the same 1-butanol adsorbs the most strongly, then 2-butanol, and finally butyl alcohol. The locations of adsorption were also found to be similar for all isomers 1-butanol prefers to adsorb in the sinusoidal channels, whereas 2-butanol... 

Figure 5. Temperature dependence of Xe-wall interactions for MCM-41 samples with various pore sizes. The data obtained from Xe adsorbed on silicalite (ref. 18), zeolite NaY (refs. 14, 16, 19) and on polymer surfaces (ref. 17) are also shown for comparison.

Meiler and Pfeifer (493) measured 13C and H NMR spectra of carbon monoxide, carbon dioxide, and benzene adsorbed on ZSM-5 and silicalite. The 13C signal from benzene was a superimposition of two lines corresponding to relatively mobile molecules (narrow Lorentzian line) and strongly adsorbed molecules (broad asymmetric line similar to that in polycrystalline benzene). Quantitative interpretation of the spectrum was possible via the measurement of the transverse proton relaxation times, T2, as a function of temperature and coverage. Recent work involving 13C NMR studies of sorbed species is summarized in Table XX. 

As has been mentioned in Section III,G, West (101) and Fyfe et al. (102) found that traces of adsorbed species (aromatic hydrocarbons and alkanols) radically change the 29Si MAS NMR spectrum and the XRD pattern of silicalite. It is too early to predict the potential of this fascinating discovery for the structural elucidation of zeolites, but one can speculate about the possible consequential pitfalls. One of them is the extreme sensitivity of the effect, requiring less than one molecule of sorbate per unit cell of the sorbent. Quantitative measurements will therefore have to be carried out under very... 

The high silica version of 7.SM-5, also known as silicalite. is a hydrophobic adsorbent capable of adsorbing, e.g.. ethanol from an aqueous solution. 

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