Zeolites measurement

Fig. 3.1.6 Temperature dependence of the intraparticle diffusivity of n-octane in an FCC catalyst and the intracrystalline diffusivity of n-octane in large crystals of USY zeolite measured by PFG NMR. The concentration of n-octane in the samples was in all cases 0.62 mmol g 1. Lines show the results of the extrapolation of the intracrystalline diffusivity and of the intraparticle diffusivity of n-octane to higher temperatures, including in particular a temperature of 800 K, typical of FCC catalysis.

Other materials which have been characterized by inelastic neutron scattering include silver A and 13X zeolites. Measurements of the scattering from ethylene-H4 and its partially deuteriated derivatives adsorbed by silver 13X zeolite have revealed all the three molecular librations. These were assigned to their respective axes from the deuteriation shifts.87... 

The catalytic activity of supported H-ZSM-5/Si02 zeolites, measured as conversion of isobutane with 1 g zeolite, correlates vith siuTace area showing a sharp maximum at 37 wt.% zeolite loading. Another less defined maximum... 

X- and Y-type zeolites in a Na" form were used as adsorbents The silica-alumina ratios in the X- and Y-type zeolites measured by the chemical analysis, were 2.5 and 4 9, respectively NO2 was obtained commercially and used without fiirther purification. The zeolite samples were activated at 673 K for 4 h under vacuum of lO" Torr. About 500 Torr of NO2 was admitted to the zeolite sample at room temperature... 

Figure 2.38 Acid properties of AI-ITQ-33 zeolite measured by pyridine adsorption and subsequent (attempted) desorption at increasing temperatures. On the left is plotted the hydroxyl stretching region, where (a) is the IR spectrum after thermal treatment at 673 K under vacuum and (b) is the spectrum after adsorbing pyridine followed by desorption at 423 K. On the right is shown the C-C stretching region of the adsorbed pyridine after evacuation at (c) 423, (d) 523, and (e) 623 K. Reproduced from Ref. (462).

Liang, W. Chen, S., and Peng. S., Difference of diffusivities in zeolites measured by the non-steady-state and the steady-state methods, Ind. Eng. Chem. Res., 36(5). 1882-1886 (1997). 

Measurement of spin-lattice relaxation enhancement in water and plasma solution. ) Plot of Un vs. surfactant concentration (SDS, SQS, SHDS) also lineshape analysis. ) Measurement of nitroxide adsorbed on zeolites. ) Measurement of a, in 15 solvents. Dependence of on solvent polarity and temperature measured. ) Complexes with Cu " and Co " also reported. ) ENDOR spectra of radical bound to lyophilized human oxyhaemoglobin. ) EPR measurement of signal intensity with varying temperature. ... 

Figure 2. Comparison of heats of sorption for N2 and O2 on CaA and CO2 on NaX zeolites measured with SIM (open symbols) and Tian-Calvet calorimetry (full symbols).

Nitrogen is the most widely used absorbent (at 77 K) for the BET method and has been employed almost universally. Argon is more suited to the measurement of microporous zeolites. Krypton may be used for the... 

Alongside tliese teclmiques, microbalance measurements of adsorjDtion capacities and kinetics, microcalorimetric measurements of adsorjDtion processes and temperature-programmed desorjDtion of base molecules have provided useful infonnation about tire tliennochemistry of adsorjDtion processes and tire acidity characteristics of zeolites [46]. 

Zeolites and Catalytic Cracking. The best-understood metal oxide catalysts are zeoHtes, ie, crystalline aluminosihcates (77—79). The zeoHtes are well understood because they have much more nearly uniform compositions and stmctures than amorphous metal oxides such as siUca and alumina. Here the usage of amorphous refers to results of x-ray diffraction experiments the crystaUites of a metal oxide such as y-Al202 that constitute the microparticles are usually so small that sharp x-ray diffraction patterns are not measured consequendy the soHds are said to be x-ray amorphous or simply amorphous. 

Dissolved Solids None Dissolved solids is measure of total amount of dissolved matter, determined by evaporation high concentrations of dissolved solids are objectionable because of process interference and as a cause of foaming in boilers Various softening processes, such as lime softening and cation exchange by hydrogen zeolite, will reduce dissolved, solids demineralization distillation reverse osmosis electrodialysis... 

In particular, emphasis will be placed on the use of chemisorption to measure the metal dispersion, metal area, or particle size of catalytically active metals supported on nonreducible oxides such as the refractory oxides, silica, alumina, silica-alumina, and zeolites. In contrast to physical adsorption, there are no complete books devoted to this aspect of catalyst characterization however, there is a chapter in Anderson that discusses the subject. 

Mcntasty el al. [35] and others [13, 36] have measured methane uptakes on zeolites. These materials, such as the 4A, 5A and 13X zeolites, have methane uptakes which are lower than would be predicted using the above relationship. This suggests that either the zeolite cavity is more attractive to 77 K nitrogen than a carbon pore, or methane at 298 K, 3.4 MPa, is attracted more to a carbon pore than a zeolite. The latter proposition is supported by the modeling of Cracknel et al. [37, 38], who show that methane densities in silica cavities will be lower than for the equivalent size parallel slit shaped pore of their model carbon. Results reported by Ventura [39] for silica xerogels lead to a similar conclusion. Thus, porous silica adsorbents with equivalent nitrogen derived micropore volumes to carbons adsorb and deliver less methane. For delivery of 150 V./V a silica based adsorbent would requne a micropore volume in excess of 0.70 ml per ml of packed vessel volume. 

A good catalyst is also stable. It must not deactivate at the high temperature levels (1300 to 1400°F) experienced in regenerators. It must also be resistant to contamination. While all catalysts are subject to contamination by certain metals, such as nickel, vanadium, and iron in extremely minute amounts, some are affected much more than others. While metal contaminants deactivate the catalyst slightly, this is not serious. The really important effect of the metals is that they destroy a catalyst s selectivity. The hydrogen and coke yields go up very rapidly, and the gasoline yield goes down. While Zeolite catalysts are not as sensitive to metals as 3A catalysts, they are more sensitive to the carbon level on the catalyst than 3A. Since all commercial catalysts are contaminated to some extent, it has been necessary to set up a measure that will reflect just how badly they are contaminated. 

Unit Cell Size (UCS). The UCS is a measure of aluminum sites or the total potential acidity per unit cell. The negatively-charged aluminum atoms are sources of active sites in the zeolite. Silicon atoms do not... 

The reported surface area is the combined surface area of zeolite and matrix. In zeolite manufacturing, the measurement of the zeolite surface area is one of the procedures used by catalyst suppliers to control quality. The surface area is commonly determined by the amount of nitrogen adsorbed by the catalyst. 

For an identical fresh catalyst, the surface area of an E-cat is an indirect measurement of its activity. The SA is the sum of zeolite and... 

Electrochemical studies, in combination with EPR measurements, of the analogous non-chiral occluded (salen)Mn complex in Y zeoUte showed that only a small proportion of the complex, i.e., that located on the outer part of the support, is accessible and takes part in the catalytic process [26]. Only this proportion (about 20%) is finally oxidized to Mn and hence the amount of catalyst is much lower than expected. This phenomenon explains the low catalytic activity of this system. We have considered other attempts at this approach using zeolites with larger pore sizes as examples of cationic exchange and these have been included in Sect. 3.2.3. 

When NOj levels are measured electrochemicaUy, NO and NO2 can lead to opposing signals because NO is oxidized and NO2 tends to be reduced. Moreover, it is preferred to obtain a total NO, measurement instead of only one of the constituents. The latter can be achieved by catalytically equilibrating the feed with oxygen before contact with the sensor by coating an active zeolite layer on top or placing a active catalyst bed in front of the sensor. Both approaches have been demonstrated successfully with a Pt-Y zeohte as active catalyst [74, 75]. The additional advantage of the filter bed is a reduction in the cross-sensitivity with CO due to CO oxidation above 673 K. 

As surface area and pore structure are properties of key importance for any catalyst or support material, we will first describe how these properties can be measured. First, it is useful to draw a clear borderline between roughness and porosity. If most features on a surface are deeper than they are wide, then we call the surface porous (Fig. 5.16). Although it is convenient to think about pores in terms of hollow cylinders, one should realize that pores may have all kinds of shapes. The pore system of zeolites consists of microporous channels and cages, whereas the pores of a silica gel support are formed by the interstices between spheres. Alumina and carbon black, on the other hand, have platelet structures, resulting in slit-shaped pores. All support materials may contain micro, meso and macropores (see text box for definitions). 

---