Zeolites critical properties

The recovery of petroleum from sandstone and the release of kerogen from oil shale and tar sands both depend strongly on the microstmcture and surface properties of these porous media. The interfacial properties of complex liquid agents—mixtures of polymers and surfactants—are critical to viscosity control in tertiary oil recovery and to the comminution of minerals and coal. The corrosion and wear of mechanical parts are influenced by the composition and stmcture of metal surfaces, as well as by the interaction of lubricants with these surfaces. Microstmcture and surface properties are vitally important to both the performance of electrodes in electrochemical processes and the effectiveness of catalysts. Advances in synthetic chemistry are opening the door to the design of zeolites and layered compounds with tightly specified properties to provide the desired catalytic activity and separation selectivity. 

Chemical and electrochemical techniques have been applied for the dimensionally controlled fabrication of a wide variety of materials, such as metals, semiconductors, and conductive polymers, within glass, oxide, and polymer matrices (e.g., [135-137]). Topologically complex structures like zeolites have been used also as 3D matrices [138, 139]. Quantum dots/wires of metals and semiconductors can be grown electrochemically in matrices bound on an electrode surface or being modified electrodes themselves. In these processes, the chemical stability of the template in the working environment, its electronic properties, the uniformity and minimal diameter of the pores, and the pore density are critical factors. Typical templates used in electrochemical synthesis are as follows ... 

In order to compare a number of different zeolite preparations we have found it convenient to determine not the diffusivity of o-xylene per se, but to characterize the samples by measuring the time (tQ 3) it takes to sorb 30% of the quantity sorbed at infinite time. The characteristic diffusion time, t0 3, is a direct measure of the critical mass transfer property r2/D ... 

Of the various mechanical properties of a formed catalyst containing zeolite, attrition resistance is probably the most critical. This is particularly the case for FCC catalysts because of the impact on the addihon rate of fresh catalyst, particulate emissions of fines and overall catalyst flow in the reactor and regenerator. Most attrition methods are a relative determination by means of air jet attrition with samples in the 10 to 180 xm size range. For example the ASTM D5757 method attrites a humidified sample of powder with three high velocity jets of humidified air. The fines are continuously removed from the attrition zone by elucidation into a fines collection assembly. The relative attrition index is calculated from the elutriated fines removed at a specific time interval. 

When developing a liquid phase adsorptive separation process, a laboratory pulse test is typically used as a tool to search for a suitable adsorbent and desorbent combination for a particular separation. The properties of the suitable adsorbent, such as type of zeolite, exchange cation and adsorbent water content, are a critical part of the study. The desorbent, temperature and liquid flow circulation are also critical parameters that can be obtained from the pulse test. The pulse test is not only a critical tool for developing the equilibrium-selective adsorption process it is also an essential tool for other separation process developments such as rate-selective adsorption, shape-selective adsorption, ion exchange and reactive adsorption. 

There are many different zeolite structures but only a few have been studied extensively for membrane applications. Table 10.1 lists some of these structures and their basic properties. One of the most critical selection criterion when choosing a zeolite for a particular application is the pore size exhibited by the material. Figure 10.1 compares the effective pore size of the different zeolitic materials with various molecule kinetic diameters. Because the pores of zeolites are not perfectly circular each zeolite type is represented by a shaded area that indicates the range of molecules that may stiU enter the pore network, even if they diffuse with difficulty. By far the most common membrane material studied is MFI-type zeolite (ZSM-5, Al-free siUcahte-l) due to ease of preparation, control of microstructure and versatility of applications [7]. 

Supported noble metal catalysts (Pt, Pd, Ag, Rh, Ni, etc.) are an important class of catalysts. Depositing noble metals on high-area oxide supports (alumina, silica, zeolites) disperses the metal over the surface so that nearly every metal atom is on the surface. A critical property of supported catalysts is that they have high dispersion (fraction of atoms on the surface), and this is a strong function of support, method of preparation, and treatment conditions. Since noble metals are very expensive, this reduces the cost of catalyst. It is fairly common to have situations where the noble metals in a catalyst cost more than 100,000 in a typical reactor. Fortunately, these metals can usually be recovered and recycled when the catalyst has become deactivated and needs to be replaced. 

The object of this paragraph is not to give a comprehensive overview of zeolites but mainly to highlight definitions and properties critical to the forthcoming discussion. A useful introduction is the subject of Chapter 1 of this book and more detailed information can be found in the references therein. 

The substitution of aluminium for boron in zeolites leads to a material with decreased Broensted acidity. These properties have been successfully applied in industrial processes, such as the Assoreni (methyl tertiobuthylether into methanol and isobutene) and Amoco processes (xylene isomerization and ethylbenzene conversion) [1-3]. Recently, the methanol conversion, the alkylation of toluene with methanol and the xylene isomerization on borosilicalites were critically analyzed [4]. 

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