Oxidative reactions, zeolite membrane

Membranes with extremely small pores ( < 2.5 nm diameter) can be made by pyrolysis of polymeric precursors or by modification methods listed above. Molecular sieve carbon or silica membranes with pore diameters of 1 nm have been made by controlled pyrolysis of certain thermoset polymers (e.g. Koresh, Jacob and Soffer 1983) or silicone rubbers (Lee and Khang 1986), respectively. There is, however, very little information in the published literature. Molecular sieve dimensions can also be obtained by modifying the pore system of an already formed membrane structure. It has been claimed that zeolitic membranes can be prepared by reaction of alumina membranes with silica and alkali followed by hydrothermal treatment (Suzuki 1987). Very small pores are also obtained by hydrolysis of organometallic silicium compounds in alumina membranes followed by heat treatment (Uhlhom, Keizer and Burggraaf 1989). Finally, oxides or metals can be precipitated or adsorbed from solutions or by gas phase deposition within the pores of an already formed membrane to modify the chemical nature of the membrane or to decrease the effective pore size. In the last case a high concentration of the precipitated material in the pore system is necessary. The above-mentioned methods have been reported very recently (1987-1989) and the results are not yet substantiated very well. 

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. 

It seems that zeolite membranes may not be the best choice as catalytic contactors and oxygen distributors to enhance selectivity in oxidative dehydrogenation of propane. This may be due in part to the intrinsic catalytic activity of the zeolite material for this reaction, which probably exerts a nonselective contribution. Therefore, this specific application operates at conditions that do not make use of the most important properties, which are characteristic of zeolite membranes. More efficient approaches for selectivity enhancement can be obtained with zeolite membranes, as shown in the next section. 

A common feature of all catalysis for F-T synthesis, whether they are cobalt or iron based, is that the catalytic activity is reduced due to the oxidation of active species. Under the typical reaction conditions, this oxidation may be caused by water, which is one of the primary products in the F-T process. On the other hand, at low partial pressure water can also help to increase the product quality by increasing the chain growth probability. Thus, in situ removing some of the water from the product and keeping the water pressure at an optimal value may improve the catalysis activity and promote the reaction rate. Zhu and coworkers [22] have evaluated the potential separation using NaA zeolite membrane to in situ removal of water Irom simulated F-T product stream. High selectivity for water removal from CO, H2 and CH4 were obtained. This result opened an opportunity for in situ water removal from F-T synthesis under the reaction conditions. 

In catalytic membrane reactors (CMRs), the reactions take place directly on the membrane and the membrane functions as both a catalyst and a separator/distributor.This requires that the membrane material has intrinsic catalytic activity or that it is modified by the addition of active components. Some of the commonly utilized inorganic (such as metal oxide and zeolite) and metal membranes are intrinsically catalytically active. In other cases, the catalysts can be integrated with the membrane into a single body by being coated on the membrane surface or deposited inside the membrane porous structure. In case the membrane does not participate in the reaction directly, but is used to add or remove certain species from the reactor, this is called an inert membrane reactor (IMR). 

As mentioned in Chapter 1, the catalyst in porous MRs may just be placed on the membrane (illustrated in Figure 1.12(a)). The reaction takes place in the catalyst phase and the membrane only serves either as a product extractor or as a reactant distributor but does not participate directly in chemical reactions. It is not always easy to obtain a true inert membrane since the porous membrane materials such as alumina, silica, titania, zirconia, zeolite or the components used to modify membrane permeation properties (e.g., pore-filling materials) can make a contribution to reactions. In order to reduce non-selective catalytic activity, the membrane used in selective oxidation reactions often has to be modified significantly by using controlled sintering to reduce surface area, or by doping with alkaline compounds to decrease surface acidity [19]. 

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