Zeolite-based membranes supports

Controlled removal of the template is especially important when zeolite based membranes are involved consisting of a continuous MFI layer on a ceramic or sintered metal support (ref. 14). In these novel composite ceramic membranes the formation of cracks during template removal would be detrimental. The unique properties (ref. 14) of metal-supported MFl-layer membranes prove that indeed crack formation can be essentially prevented. 

During the last few years, ceramic- and zeolite-based membranes have begun to be used for a few commercial separations. These membranes are all multilayer composite structures formed by coating a thin selective ceramic or zeolite layer onto a microporous ceramic support. Ceramic membranes are prepared by the sol-gel technique described in Chapter 3 zeolite membranes are prepared by direct crystallization, in which the thin zeolite layer is crystallized at high pressure and temperature directly onto the microporous support [24,25],... 

The first reported zeolite-based membranes were composed of zeolite-filled polymers [3-9]. The incorporation of zeolite crystals into these polymers resulted in a change of both permeation behavior and selectivity, due to the alteration of the affinity of the membrane for the components studied. Up to now, most known inorganic, zeolitic membranes have consisted of supported or unsupported ZSM-5 or silicalite [10-27]. Other reported membranes are prepared from zeolite-X [21], zeolite-A [21,28], or AIPO4-5 [29]. The materials used as support arc metals, glass, or alumina. The membrane configurations employed are flat sheet modules and annular tubes. 

Zeolites are erystaUine nanoporous materials with uniform nanosized pores (<1 nm) (Fig. 9.3). Selective permeation in zeolite membranes is based on molecular sieving and selective adsorption. Zeolite membranes have drawn attention as suitable membranes for DH applications due to their high thermal and chemical stability. When supported (Fig. 9.3), zeolite-based membranes also offer excellent mechanical strength, which is an important feature for DH applications. The permeation of single compounds in zeolitic membranes depends on the kinetic diameter of the molecule and size selectivity and they exhibit moderate selectivities to hydrogen. 

As can be seen in Table 19.2, and with some more details in Table 19.3 (this last table shows a short list of some relevant membranes used in the ethyl acetate production research together with separation factors and fluxes obtained), zeolite-based membranes (mordenite and zeolite A) were also tested by De La Iglesia et al. (2007) in an ISU-type continuous membrane reactor packed with Amberlyst 15. Both membranes were capable of shifting the equilibrium (in <1 day) and, in particular, mordenite membranes allowed conversions of approximately 90% and high separation factors of H20/ethanol and H20/acetic acid (>170). Moreover, because of the lower content in aluminum, under acid conditions, mordenite membranes were more stable than zeolite A. Hence, mordenite was also used by De La Iglesia et al. (2006), in another work, to prepare two-layered mordenite-ZSM-5 composite membranes, as shown in Figure 19.15. A tubular alumina tube was used as support. As a result, the feasibility of coupling the separation characteristics of the mordenite layer with the catalytic behavior of the H-ZSM-5 layer was demonstrated. 

The in situ membrane growth technique cannot be applied using the zeolite-based ceramic porous membrane as support, under hydrothermal conditions in a solution containing sodium hydroxide. The high pH conditions will cause membrane amorphization and lead to final dissolution. Therefore, we tried to synthesize an aluminophosphate zeolite such as AlP04-5 [105] over a zeolite porous ceramic membrane. For the synthesis of the AlP04-5-zeolite-based porous membrane composite, the in situ membrane growth technique [7,13,22] was chosen. Then, the support, that is, the zeolite-based porous ceramic membrane, was placed in contact with the synthesis mixture and, subsequently, subjected to a hydrothermal synthesis process [18]. The batch preparation was as follows [106] ... 

It is evident that the ceramic membrane, which is represented in the XRD pattern (see Figure 10.6) by the amorphous component of the XRD profile, was covered by the AlP04-5 molecular sieve, since the crystalline component of the obtained XRD pattern fairly well coincides with the standards reported in the literature [107]. Consequently, the porous support was successfully coated with a zeolite layer, which was shaped by the hydrothermal process as previously described. Thus, a composite membrane, that is, an AlP04-5 molecular sieve thin film zeolite-based ceramic, was produced. 

Silicalite-1, are known to grow relatively easy on various surfaces, Moreover, some principles have been developed by Jansen et al. [8] how to govern the zeolite crystal orientation with respect to the support. Two articles with a reviewing character [7,44] as to MFI-based membranes are recommended to the reader. 

Hardly any research has been performed on ferrierite in zeolite membrane configurations. Matsukada et al. [50,51] prepared a ferrierite-based membrane by the frequently used Vapour-phase Transport Method. By using ethylenediamine, triethylamine and steam (under hydrothermal conditions), a porous alumina support, covered with the proper aluminosilicate gel, was transformed into a alumina supported (30 pm thick) ferrierite layer. No permeation with 1,3,5-triisopropylbenzene coirld be observed, proving the layer to be defect-free. Fluxes of small gases were found in the order of 10" -10 mol.m. s. Pa and decreased in the order H2>He>CH4>N2>02>C02... 

In the supported systems the catalyst can be coated on the walls of the reactor, supported on a solid substrate or deposited around the case of the light source. Many are the supported materials used in literature, such as glass beads, and tubes [69], silica-based materials [70], hollow beads, membranes [71], optical fibers, zeolites, activated carbon, organic fibers [72], and so on. 

Membranes are classified as organic or inorganic, taking into account the material used for their syntheses porous or dense, based on the porosity of the material applied and symmetric and asymmetric for a membrane made of a single porous or dense material or for a membrane made of a porous support and a dense end, respectively [16,64], We are fundamentally interested here in asymmetric inorganic membranes made of a porous end to bring mechanical stability to the membrane and made of alumina, silica, carbon, zeolites, and other materials, and a dense end to give selectivity to the membrane (see Chapter 10). However, we also analyze the performance of porous polymers. 

Nevertheless, the availability of procedures allows the preparation of zeolite membranes and layers with sufficient quality, reproducibility, and reliability only up to a few hundred square centimeters in surface, delaying the industrial implementation of zeolite membrane-based technology. To be realistic, the lack of module reliability under extreme temperature cycling or harsh environment and the necessary raw material cost reductions (supports and chemicals) are two of the main challenges toward which strong efforts must be targeted. 

In asymmetric supported membranes the use of permeability data can give rise to much confusion and erroneous conclusions for several reasons. In most cases the layer thickness is not precisely known and usually it is not known whether this layer is homogeneous or has property gradients (e.g. a "skin" and a more porous part). In many cases the material of the layer penetrates the support to some extent and so it is not possible to separate properties of separation layer and support without giving account of the interface effect. Finally, even if all these complications can be avoided, a comparison based on separation layer properties expressed in terms of permeabilities can give a completely wrong impression of the practical possibilities (as done in e.g. Ref. [109]). This is illustrated by comparison of hydrogen permeabilities of ultra-thin silica layers (see Tables 9.14-9.16) with other materials such as zeolites and metals. The "intrinsic" material properties of these silica layers are not impressive ... 

The purpose in showing these rather exotic structures is to indicate the many possibilities for selectivity for shapes,79 some of which are not possible with zeolites, pillared clays, on others. Sometimes, the host structure adjusts to the guest to give an induced fit. By using this method, it is possible to select compounds based solely on size. For practical use, it may often be necessary to immobilize these structures on supports or place them in membranes. 

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