Zeolite membrane reactors

In the case of a catalytic membrane reactor (CMR), the membrane is (made) intrinsically catalytically active. This can be done by using the intrinsic catalytic properties of the zeolite or by making the membrane catalytically active. When an active phase is deposited on top of a membrane layer, this is also called a CMR because this becomes part of the composite membrane. In addition to the catalytic activity of the membrane, a catalyst bed can be present (PBCMR). The advantages of a CMR are as follows ... 

Table 10.2 Performance of several zeolite membrane reactors in the xylene isomerization reaction. 

Modeling on the reactor level, which is needed in designing the zeolite membrane reactor, could receive some more attention, since the number of studies in this particular field are few [56,106]. 

Hong, M., R.D. Noble, and J.L. Falconer, Highly selective H2 Separation Zeolite Membranes for Coal Gasification Membrane Reactor Applications, Annual Technical Progress Report, U.S. DOE Contract DE-FG26-02NT41536, December 2005. 

Lin, J.Y.S., Zeolite Membrane Reactor for Water-Gas-Shift Reaction for Hydrogen Production, Proceedings of2007 U.S. DOE Hydrogen Annual Merit Review Meeting, Arlington, VA, May 2007. 

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 a packed-bed membrane reactor (PBMR) the membrane is permselective and removes the product as it is formed, forcing the reaction to the right. In this case, the membrane is not active and a conventional catalyst is used. Tavolaro et al. [45] demonstrated this concept in their work on CO2 hydrogenation to methanol using a LTA zeolite membrane. The tubular membrane was packed with bimetallic Cu/ZnO where CO2 and H2 react to form EtOH and H2O. These condensable products were removed by LTA membrane which increased the reaction yield when compared to a conventional packed bed reactor operating under the same conditions [45]. 

One of the main challenges for zeolite membrane reactors is that optimal reactor operation requires that the membrane flux be in balance with the reaction rate.. Whether acting in an inert or catalytic capacity, the extractive ability of the membrane needs to keep up with the production of the species being removed in order to fully participate in improving the reaction yield [44]. 

McLeary, E.E., Jansen, J.C., and Kapteijn, E. (2006) Zeolite based films, membranes and membrane reactors progress and prospects. Micropor. Mesopor. Mater., 90,198-220. 

Tavalaro, A. and Tavolaro, P. (2007) LTA zeolite composite membrane preparation, characterization and application in a zeohtic membrane reactor. Catal. Commun., 8, 789-794. 

M., Mukai, S.R., Kawase, M., and Hashimoto, K. (2003) Methanol to olefins using ZSM-5 zeolite catalyst membrane reactor. Chem. Eng. Sci.,... 

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],... 

A FePc complex encaged in the zeolite Y supercages, in its turn, can be wrapped in a polydimethylsiloxane membrane, thus acting not only as a mechanistic but also as a formal mimic of Cytochrome P450 often found in cell membranes.[57] Such membranes, contacted on one side with substrate and on the other side with oxidant, catalyse oxygenation reactions in a membrane reactor in the absence of any solvent, the majority of the product amount being recovered from the more polar phase. 

The book explores various examples of these important materials, including perovskites, zeolites, mesoporous molecular sieves, silica, alumina, active carbons, carbon nanotubes, titanium dioxide, magnesium oxide, clays, pillared clays, hydrotalcites, alkali metal titanates, titanium silicates, polymers, and coordination polymers. It shows how the materials are used in adsorption, ion conduction, ion exchange, gas separation, membrane reactors, catalysts, catalysts supports, sensors, pollution abatement, detergency, animal nourishment, agriculture, and sustainable energy applications. 

Recent results on isobutane dehydrogenation have been reported, and a conventional reactor has been compared with membrane reactors consisting of a fixed-bed Pt-based catalyst and different types of membrane [51]. In the case of a mesoporous y-AKOi membrane (similar to those used in several studies reported in the literature), the observed increase in conversion could be fully accounted for simply by the decrease in the partial pressures due to the complete mixing of reactants, products and sweep gas. When a permselective ultramicroporous zeolite membrane is used, this mixing is prevented the increase in conversion (% 70%) can be attributed to the selective permeation of hydrogen shifting the equilibrium. 

The ultimate design of an inert membrane reactor would consist of well chosen crack free zeolite film membranes. The difficulties in this case are even more deterrent for industrial scale reactors since only a small number of holes or cracks would ruin the potential advantages of the design. 

Zaspalis et al. [1991b] and Bitter [1988] utilized alumina membrane reactors containing Pt catalysts to examine dehydrogenation of n-butane to butene and 2-methylbutenes to isoprene, respectively. Both the conversion and selectivity improved by using the membrane reactors. The increase of conversion is about 50% in both cases. Moreover, Suzuki [1987] used stainless steel membranes and Pi or CaA-zeolite layer catalysts to perform dehydrogenation of isobutene and propene to produce propane. 

Section 6 will deal with theory and practise of permeation through zeolite membranes, and finally examples will be given of the use of zeolites in membrane reactors and catalytic membranes. 

Zeolite membranes may play either a passive or an active role in catalytic (organic) conversion reactions and the potential applications of zeolite membrane reactors are quite promising. Both liquid phase and gas phase reactions may advantageously be carried out in a membrane reactor, and transport from the reaction zone is promoted by continuous removal of the permeating molecules. 

A type a example is given in the Mobil patent mentioned above [86], The membrane reactor having the configuration as described before, was equipped with a K-exchanged ZSM-5 membrane having a Si/Al ratio of 220. The membrane was impregnated with chloroplatinic acid to give 0.001 wt% Pt based on total quantity of zeolite of zeolite, and reduced at 500 C in... 

The insertion of catalytically active guests, such as transition metal ions, is an example of the potentialities of zeolite membranes for applications in catalytic membrane reactors. The well-known catalytic properties of supported vanadium oxides for selective oxidations have recently prompted a number of studies on the possibility of inserting vanadium in the framework of crystalline microporous silica and aluminosilicate powders. " ... 

However, at least for separative applications, most hopes to find consistent application of inorganic-membrane reactors lie in the development of inorganic membranes having pores of molecular dimensions (<10 A, e.g., zeolitic membranes). Such membranes should moreover be thin enough to allow reasonable permeability, defect-free, resilient, and stable from the thermal, mechanical, and chemical standpoints. Such results should not be achieved only at a lab scale (a lot of promising literature has recently appeared in this context), but should also be reproducible at a large, industrial scale. Last, but not least, such membranes should not be unacceptably expensive, in both their initial and their replacement costs. 

The combination of reaction and separation in one multifunctional membrane reactor is an interesting option. In such a reactor the membrane could be catalytically active itself, or it could serve only as a separation medium. There are several types of operation for such a reactor [33]. It could be used to separate the formed products from the reaction mixture. In this way it is possible to overcome equilibrium limitations or to improve the selectivity of the reaction. Another possibility is the controlled addition of reactant via the membrane, which might be of use in, for example, oxidation reactions or sequential reactions. The advantage of using zeolitic membranes in a membrane reactor is that they have a high thermal stability and exhibit a good selectivity. Moreover, they can be made catalytically active. 

Zeolite-Membrane Reactors for Conversion Enhancement by Product Removal.298... 

Zeolite-Membrane Reactors as Reactant Distributors for Selectivity Enhancement.301... 

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