Zeolite-based membranes preparation

ZEOLITE-BASED MEMBRANES PREPARATION, PERFORMANCE AND PROSPECTS... 

Chapter 12. Zeolite-based Membranes, Preparation, Performance and Prospects... 

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. 

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] ... 

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... 

Zeolite materials are used commercially as shape/ size selective catalysts in the petrochemical and petroleum refining industry, and as molecular sieving separation media for gases and hydrocarbons. For both applications, zeolites are used in powder composite form such as pellets and granules. In this entry, we focus on zeolite membranes. We define zeolite membranes as a continuous phase of zeolite-based materials (pure zeolite or composite) that separate two spaces. Zeolite membranes are generally uniform thin films attached to a porous or a nonporous substrate. They can also be self-standing without a substrate. Note that we have included zeolite films and layers on nonporous substrate in this entry because we believe many of the synthesis strategies and applications reported for those nonporous substrates are easily transferred to a porous substrate to prepare a zeolite membrane. 

Zeolite NaA and FAU crystals were grown under the same hydrothermal condition using the same composition of clear solution. The only difference was the type of seed crystal used. This result suggested that the crystal growth did not occur by the attachment of nano-crystals. Zeolite films/membranes were prepared by the growth of seeded crystals. Based on the SEM and TEM observations and single gas permeation measurements, densification model of film/membrane is presented. 

Membranes with promising properties have been prepared from polyphosp-hazenes in combination with sulfonimide (polyphosphazene-based sulfonimide Chalkova et al., 2002) or with polyacrylonitrile (blended polyphosp-hazene/polyacrylonitrile Carter et al., 2002). Low methanol crossover was also seen with membranes prepared from poly(vinyl alcohol) that contained mordenite (a zeolite variety Libby et al., 2001). Various aspects of the work on composite membranes prepared from different polymers have been discussed in detail in a review by Savadogo (2004). 

Another potential application for zeolite/polymer mixed-matrix membranes is the separation of various liquid chemical mixtures via pervaporation. Pervapora-tion is a promising membrane-based technique for the separation of liquid chemical mixtures, especially in azeotropic or close-boihng solutions. Polydime thy 1-siloxane (PDMS), which is a hydrophobic polymer, has been widely used as the continuous polymer matrix for preparing hydrophobic mixed-matrix membranes. To achieve good compatibility and adhesion between the zeolite particles and the PDMS polymer, ZSM-5 was incorporated into the PDMS polymer matrix, the resulting ZS M -5/ P DM S mixed-matrix membranes showed simultaneous enhancement in selectivity and flux for the separation of isopropyl alcohol from water. It was demonstrated that the separation performance of these membranes was affected by the concentration of the isopropyl alcohol in the feed [96]. 

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. 

The CS-based mixed matrix membranes are also suitable for pervaporation application. Patil and Aminbhavi [96] prepared mixed matrix membranes of CS by incorporating sili-calite zeolite particles in 5 and 10 wt.% for the pervaporation separation of toluene/methanol and toluene/ethanol feeds in compositions of 10-40 wt.% of toluene at 30°C. The membranes were toluene selective than alcohol selective. Flux of toluene/methanol and toluene/ethanol mixtures decreased, but selectivity increased with increasing alcohol content of the feed. Toluene permeated preferentially with a selectivity of 264 and fluxes of 0.019-0.027 kg/m h for toluene/ methanol mixture. Selectivity of 301 with fluxes ranging from 0.019 to 0.026 kg/m h was observed for tolnene/etha-nol mixtures. Flux increased, while selectivity decreased with increasing toluene content of the feeds. An increase in silicalite content of the MMMs gave increased pervaporation performances. 

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