Zeolite permeation

As have been seen above adsorption plays an important role in permeation through microporous membranes. So, single and multicomponent adsorption isotherms are required for a successful modelling of the permeation behaviour. An extensive treatment of the recent state of the art of zeolite permeation modelling is given by Van de Graaf et al. [70]. A shortened treatment follows here. 

The more permeable component is called the. st ga.s, so it is the one enriched in the permeate stream. Permeability through polymers is the product of solubihty and diffusivity. The diffusivity of a gas in a membrane is inversely proportional to its kinetic diameter, a value determined from zeolite cage exclusion data (see Table 22-23 after Breck, Zeolite Molecular Sieves, Wiley, NY, 1974, p. 636). 

Zeolite A is a very successful membrane for separation of water from alcohols, but it suffers from stability issues under acid conditions [23]. Usually, a Hquid phase should be avoided and, for this reason, vapor permeation is preferred. Recent developments show that the hydrophilic MOR [23] and PHI [50] membranes are more stable under acidic conditions in combination with a good membrane performance. 

The consideration that many zeolite types exist, each with many tunable properties (e.g., pore size and alumina content), leads not only to a wealth of options but also to a high level of complexity. Owing to this complexity and limited understanding of zeolite formation and permeation behavior, a lot of experimental effort is required in this field, slowing down developments toward successful application. 

Figure 9. H2 ( ) / n-butane ( ) separaticm with the ccxnposite zeolite-alumina membrane (fluxes in the permeate as a function of the tenq>erature). A mixture of hydrogen, n-btitane and nitrogen (12 14 74) was fed in the tube (Fig. 2) with a flow rate of 4.8 1/h. Sweep gas (N2), countercurrent mode, flow rate 4.3 1/h.

Molecular sieving effect of the membrane has been evidenced using a mixture of two isomers (i.e. no Knudsen separation can be anticipated), n-hexane and 2-2 dimethylbutane (respective kinetic diameters 0.43 and 0.62 nm). Figure 10 shows the permeate contains almost only the linear species, due to the sieving effect of the zeolite membrane (pore size ca 0.55 nm). This last result also underlines that the present zeolite membrane is almost defect-fi ee. 

At low temperatures, adsorptive separation becomes important for zeolite membranes as sorption of one species can effectively hinder permeation of other species. 

Some bead materials possess porous structure and, therefore, have very high surface to volume ratio. The examples include silica-gel, controlled pore glass, and zeolite beads. These inorganic materials are made use of to design gas sensors. Indicators are usually adsorbed on the surface and the beads are then dispersed in a permeation-selective membrane (usually silicone rubbers). Such sensors possess high sensitivity to oxygen and a fast response in the gas phase but can be rather slow in the aqueous phase since the gas contained in the pores needs to be exchanged. Porous polymeric materials are rarer and have not been used so far in optical nanosensors. 

S., Fiaty, K., and Dalmon, J.-A. (2000) Experimental smdy and numerical simulation of hydrogen/isobutane permeation and separation using MFI-zeolite membrane reactor. Catal. Today, 56 (1-3), 253-264. 

For single-component gas permeation through a microporous membrane, the flux (J) can be described by Eq. (10.1), where p is the density of the membrane, ris the thermodynamic correction factor which describes the equilibrium relationship between the concentration in the membrane and partial pressure of the permeating gas (adsorption isotherm), q is the concentration of the permeating species in zeolite and x is the position in the permeating direction in the membrane. Dc is the diffusivity corrected for the interaction between the transporting species and the membrane and is described by Eq. (10.2), where Ed is the diffusion activation energy, R is the ideal gas constant and T is the absolute temperature. 

In diffusion-controlled permeation, the components in a mixture differ largely in size but none is excluded from the pore network [8]. Separation is determined by the relative diffusivity (mobility) of a component within the zeolite. Expression of this mechanism requires low to medium loadings of the pore network where molecule-molecule interactions do not hinder diffusion. At high loadings, the mobility of aU molecules is reduced and they become unable to pass one another in the pore network [8]. 

Figure 10.6 Temperature dependency of gas permeances for unmodified MFI-type zeolite membrane (closed symbols on solid line gas permeances for single permeation, open...

O Brien-Abraham, J., Kanezashi, M., and tin, Y.S. (2007) A comparative smdy on permeation and mechanical properties of random and oriented MFI-type zeolite membranes, Mesop. Microp. Mater., 105, 140-148. 

Kanezashi, M., O Brien-Abraham,)., Lin, Y.S., and Stmiki, K. (2008) Gas permeation through DDR-type zeolite membranes at high temperamres. AIChE J., 54, 1478-1486. 

Kanezashi, M. and lin, Y.S. (2009) Gas permeation and diffusion characteristics of MFI-type zeolite membranes at high temperatures. J. Chem. Phys. C, 113, 3767-3774. 

Burggraaf A.J. (1999) Single gas permeation of thin zeolite (MFI) membranes theory and analysis of... 

Zeolites used for the preparation of mixed-matrix membranes not only should have suitable pore size to allow selective permeation of a particular molecular component, but also should have appropriate particle size in the nanometer range... 

Geong and coworkers reported a new concept for the formation of zeolite/ polymer mixed-matrix reverse osmosis (RO) membranes by interfacial polymerization of mixed-matrix thin films in situ on porous polysulfone (PSF) supports [83]. The mixed-matrix films comprise NaA zeoHte nanoparticles dispersed within 50-200 nm polyamide films. It was found that the surface of the mixed-matrix films was smoother, more hydrophilic and more negatively charged than the surface of the neat polyamide RO membranes. These NaA/polyamide mixed-matrix membranes were tested for a water desalination application. It was demonstrated that the pure water permeability of the mixed-matrix membranes at the highest nanoparticle loadings was nearly doubled over that of the polyamide membranes with equivalent solute rejections. The authors also proved that the micropores of the NaA zeolites played an active role in water permeation and solute rejection. 

For the detailed study of reaction-transport interactions in the porous catalytic layer, the spatially 3D model computer-reconstructed washcoat section can be employed (Koci et al., 2006, 2007a). The structure of porous catalyst support is controlled in the course of washcoat preparation on two levels (i) the level of macropores, influenced by mixing of wet supporting material particles with different sizes followed by specific thermal treatment and (ii) the level of meso-/ micropores, determined by the internal nanostructure of the used materials (e.g. alumina, zeolites) and sizes of noble metal crystallites. Information about the porous structure (pore size distribution, typical sizes of particles, etc.) on the micro- and nanoscale levels can be obtained from scanning electron microscopy (SEM), transmission electron microscopy ( ), or other high-resolution imaging techniques in combination with mercury porosimetry and BET adsorption isotherm data. This information can be used in computer reconstruction of porous catalytic medium. In the reconstructed catalyst, transport (diffusion, permeation, heat conduction) and combined reaction-transport processes can be simulated on detailed level (Kosek et al., 2005). 

Table VII (51). The relevant free dimensions are often similar for zeolite and nonzeolite. Urea (free diameter 5.2 A) is like Sieve A (free diameter of windows 4.3 A) in accommodating n- but not isoparaffins. Thiourea (6.1 A) and offretite (6.3 A) have channels with similar free diameters as do 0-cyclodextrin (7-8 A) and zeolite L (7.1 X 7.8 A). In thiourea the loose fit of n-paraffins in the tunnel appears to destabilize the adducts (85, 36). The same is true of disc-shaped molecules comprising only benzenoid rings. However, if suitably bulky saturated side chains are attached (cyclohexyl-benzene or fertf-butylbenzene), then adduction readily occurs. Heterocy-clics, like unsubstituted aromatics, do not readily form adducts. Thus flat molecules also exert a destabilizing effect upon the tunnels of a circular cross section. Such stability problems do not arise with the robust, permanent zeolite structures, and this constitutes an interesting distinction. Offretite, for example, readily sorbs benzene or heterocyclics with or without alkyl side chains, provided only that they are not too large to permeate the structure.

Modeling Single-Component Permeation Through A Zeolite Membrane from Atomic-scale Principles... 

Bentone-34 has commonly been used in packed columns (138—139). The retention indices of many benzene homologues on squalane have been determined (140). Gas chromatography of C —C aromatic compounds using a Ucon B550X-coated capillary column is discussed in Reference 141. A variety of other separation media have also been used, including phthalic acids (142), liquid crystals (143), and Werner complexes (144). Gel permeation chromatography of alkylbenzenes and the separation of the Cg aromatics treated with zeolites are described in References 145—148. 

Mixed-matrix membranes have been a subject of research interest for more than 15 years [28-33], The concept is illustrated in Figure 8.10. At relatively low loadings of zeolite particles, permeation occurs by a combination of diffusion through the polymer phase and diffusion through the permeable zeolite particles. The relative permeation rates through the two phases are determined by their permeabilities. At low loadings of zeolite, the effect of the permeable zeolite particles on permeation can be expressed mathematically by the expression shown below, first developed by Maxwell in the 1870s [34],... 

Figure 8.10 Gas permeation through mixed-matrix membranes containing different amounts of dispersed zeolite particles...

---