Silicalite-1 zeolite membrane

W.J.W. Bakker, F. Kapteijn, J. Poppe, J.A. Moulijn, Permeation of a metal-supported Silicalite-1 zeolite membrane, accepted for publication in J. Membrane Sci. 

Bakker WJ, Kapteijn F, Poppe J, and Moulijn JA. Permeation characteristics of a metal-supported silicalite-1 zeolite membrane. J Membr Sci 1996 117 57-78. 

MasudaT, Otani S, Tsuji T, KitamuraM, andMukai SR. Preparation of hydrophilic and acid-proof silicalite-1 zeolite membrane and its application to selective separation of water from water solutions of concentrated acetic acid by pervaporation. Sep Purif Technol 2003 32(1-3) 181-189. 

All the above mentioned high perm-selectivity of zeolite membranes can be attributed to the selective sorption into the membranes. Satisfactory performance can be obtained by defective zeolite membranes. Xylene isomers separation by zeolite membranes compared with polymeric membranes are summarized in Table 15.4. As shown, zeolite membranes showed much higher isomer separation performances than that of polymeric membranes. Specially, Lai et al. [41] prepared b-oriented silicalite-1 zeolite membrane by a secondary growth method with a b-oriented seed layer and use of trimer-TPA as a template in the secondary growth step. The membrane offers p-xylene permeance of 34.3 x 10 kg/m. h with p- to o-xylene separation factor of up to 500. Recently, Yuan et al. [42] prepared siUcalite-1 zeolite membrane by a template-free secondary growth method. The synthesized membrane showed excellent performance for pervaporation separation of xylene isomers at low temperature (50°C). 

Zhang, C., Hong, Z., Gu, X.H., Zhong, Z.X., Jin, W.Q. and Xu, N.P. (2009) Silicalite-1 zeolite membrane reactor packed with HZSM-5 catalyst for meta-xylene isomerization. Industrial and Engineering Chemistry Research, 48, 4293 299. 

Jia et al. [1993] have prepared thin, dense pure silicalite zeolite membranes on porous ceramic supports by an in-situ synthesis method. A sol consisting of silica, sodium hydroxide, tctrapropylammonium bromide and water is prepared with thorough mixing. A ceramic support is immersed in the sol which is then heated and maintained at 180X... 

Funke, H.H., et al., Separation of hydrocarbon isomer vapors with silicalite zeolite membranes, Ind, Eng. Chem. Res., 35(5), 1575-1582 (1996). 

This paper describes the morphological and transport properties of a composite zeolite (silicalite) - alumina membrane. Some advantages obtained in combining the membrane with a conventional fixed-bed catalyst are also reported. 

Another challenging and industrially important separation that utihzes pervapo-ration through zeolite membranes is acid removal from H2O. In this case, the zeolite must have a high Si/Al ratio due to leaching of A1 by the acid. Both Ge-ZSM5 and silicalite have demonstrated significant stability and separation capability for the removal of acetic acid from H2O [35]. 

Improved selectivity in the liquid-phase oligomerization of i-butene by extraction of a primary product (i-octene C8) in a zeolite membrane reactor (acid resin catalyst bed located on the membrane tube side) with respect to a conventional fixed-bed reactor has been reported [35]. The MFI (silicalite) membrane selectively removes the C8 product from the reaction environment, thus reducing the formation of other unwanted byproducts. Another interesting example is the isobutane (iC4) dehydrogenation carried out in an extractor-type zeolite CMR (including a Pt-based fixed-bed catalyst) in which the removal of the hydrogen allows the equilibrium limitations to be overcome [36],... 

Zeolite single crystals may serve as zeolite membrane models. We mention the early elegant work of Hayhurst and Paravar [10] on an oriented large silicalite-1 crystal embedded in epoxy resin. 

MFI zeolite membranes (silicalite-1, ZSM-5), on either flat or tubular porous supports, have been the most investigated for gas separation, catalytic reactors, and pervaporation applications. The structural porosity of MFI zeolite consists of channels of about 5.5 A, in diameter, the sihca-rich compositions induce... 

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. 

The same model was applied to permeation of lighter hydrocarbons (C1-C3) through the silicalite-1 membrane [50]. In the case of methane, ethane, and ethene, some concentration dependence of the Maxwell-Stefan diffusivity was observed. This can be caused either by the importance of interfacial effects, which are not taken into account, or by the contribution of activated-gas translational diffusion to the net flux. The diffusivities calculated from these permeation experiments were, however, in rather good agreement with diffusivity values from the literature, which implies that these zeolitic membranes could also be a valuable tool for the determination of diffusion coefficients in zeolites. 

Inorganic membranes are very resistant and quite stable at hard-operating conditions. Several materials are available. Different membranes have been successfully tested for separations involving supercritical fluids such as tubular carbon membranes [ 1 ], mbular silica membranes [2-5], silica hollow fibber membranes [6], zeolite membranes [7-10], titane-nafion membranes [11], polycarbonate membrane [12], nanofilter having a thin layer of Zr02-Ti02 [12], and silicalite membranes [4]. 

In general, when carrying out a new separation, the kinetic diameter and the heat of adsorption of the gases, which compose the mixture, are the main variables used to select the most adequate zeolite. MFI, FAU, LTA, SOD, ANA, DDR, MOR, BEA, CHA, FER, KFI are zeolite structures widely used as membranes for different separations. In gas separation, MFI zeolite membranes (silicalite-1, ZSM-5, and with Al, Fe, B, and Ge isomorphously substituted into their stmctures) are the most commonly used membranes because their pores (-0.55 nm diameter) are in the size range of many industrial mixtures furthermore, their synthetic chemistry is well established in the literature. 

Based on these observations, Wang and Caruso [237] have described an effective method for the fabrication of robust zeolitic membranes with three-dimensional interconnected macroporous (1.2 pm in diameter) stmctures from mesoporous silica spheres previously seeded with silicalite-1 nanoparticles subjected to a conventional hydrothermal treatment. Subsequently, the zeolite membrane modification via the layer-by-layer electrostatic assembly of polyelectrolytes and catalase on the 3D macroporous stmcture results in a biomacromolecule-functionalized macroporous zeolitic membrane bioreactor suitable for biocatalysts investigations. The enzyme-modified membranes exhibit enhanced reaction stability and also display enzyme activities (for H2O2 decomposition) three orders of magnitude higher than their nonporous planar film counterparts assembled on silica substrates. Therefore, the potential of such structures as bioreactors is enormous. 

Zeolite monoliths have been useful for such apphcations as rotatory adsorbers for use as dehumidifiers and desiccant cooling processes [253] or in VOC treatment systems [269]. Alumina-coated sUicon carbide monoliths have also been employed as supports for B-ZSM-5 membranes [270] providing a larger surface area per unit volume, compared to traditional membrane supports. With these membranes, these authors have reported n/f-butane and H2/f-butane separation selectivities of 35 and 77, respectively [85]. Also, silicalite-1 membranes supported on stainless steel grids (Figure 10.29) have shown a good performance in the separation of n/f-butane mixtures, with separation factors as high as 53 at 63°C [255]. 

Finally, zeolite nanoparticles have been used as building blocks to construct hierarchical self-standing porous stmctures. For example, multilayers of colloidal zeolite crystals have been coated on polystyrene beads with a size of less than 10 p,m [271,272]. Also, silicalite-1 membranes with a thickness ranging from 20 to several millimeters and controlled mesoporosity [273] have been synthesized by the self-assembly of zeolite nanocrystals followed by high-pressure compression and controlled secondary crystal growth via microwave heating. These structures could be useful for separation and catalysis applications. 

Silicalite-1 membranes, supported on porous alumina ceramic discs, have been prepared by two different routes. In the first the zeolite membrane has been formed by in situ hydrothermal synthesis. Secondly a layer has been formed by controlled filtration of zeolite colloids. To optimise membrane stability, conditions have been established in which penetration of zeolite into the support sublayer occurs. The pore structure of these membranes has been characterised by a combination of SEM and Hg-porosimetry. The permeabilities of several gases have been measured together with gas mbeture separation behaviour. 

The results reported here are restricted to experiments undertaken with silicalite-1 membranes. To ensure that the developed membranes were defect free, gas relative permeability experiments were conducted. In these experiments the membrane was initially strongly equilibrated by a strongly adsorbed gas (CO2) and subsequently a non-adsorbable gas such as He permeated through the membrane. It was found that as the pre-adsorbed amount of CO2 increased there was a sharp drop in He permeability, compared to the corresponding value on a clean zeolite membrane. At a certain partial pressure of CO2, He could no longer permeate... 

The synthesis and characterisation of silicalite-1 membranes on porous alumina ceramic supports have been described here. The growth of the silicalite-1 membrane could be optimised by controlling the hydrothermal synthesis conditions. It has been shown that by controlling the synthesis conditions it is possible to optimise the growth and structure of silicalite-1 membranes. Thus at lower synthesis temperatures (150 °C), the growth of silicalite inside the macro-pores of the ceramic support is favoured. At higher temperatures (190 °C), thick, well crystallised zeolite layers develop from the surface of the support. A more stable membrane is... 

Thin zeolite membranes can also be prepared through a spin-coating process of a nanoparticle suspension. Yan and coworkers synthesized silicalite-1 and silicalite-2 in a nanoparticle suspension using a two-stage hydrothermal process.[138,139] First, the precursor... 

Defect-free zeolite membranes have so far only been produced for membranes of the MFI (silicalite type) with thicknesses of about 50 im on stainless steel supports and 3-10 pm on alumina and carbon supports. They are produced by in situ methods of zeolite crystals grown directly on the support system. There are some reports of formation of defective membranes with, e.g., zeolite A. Much more research is needed to widen the range of available zeolite membrane types especially small and wide pore systems. The permeance values of the defect-free membranes is lower than that of the amorphous membranes (see Chapter 6) and to improve this the layer thickness must be decreased together with improving the crystal quality (no impurities, no surface layers, high crystallinity, crystal orientation) and microstructure (grain boundary engineering). 

Permeation and separation data on well defined, high quality zeolite membranes are only reported for MFI (ZSM-5, silicalite) zeolites grown in situ directly from the precursor solution on top of a substrate. The experimental single gas permeation results could be in a number of cases consistently described using Eqs. (9.43)-(9.48) for the Langmuir and Henry regimes. 

---