Synthesis reactions, zeolite membrane

The crystallization of microporous compounds under microwave irradiation was developed in the 1970s, and was characterized by mild conditions, low energy consumption, rapid reaction, small particles, and uniform particle-size distribution. For example, under microwave irradiation and normal pressure, zeolite NaA could crystallize with a high crystallinity in a short time, even less than 1 minute. Thus, this new synthesis approach can quickly and continuously produce molecular sieves with low energy consumption. The microwave synthesis of zeolite NaA and microporous AIPO4-5 and the ion exchange reaction of zeolite Ce-/i will be discussed in detail later in this section. The successful synthesis of microporous FeAPC>4-5, CoAPO-5, CoAPO-44, VPI-5/771 zeolites Na-X, Na-Y, ZSM-5, and TS-1,[78] the preparation of molecular sieve membranes/791 the dispersion of salts or oxides into the channels of molecular sieves, and the modification or functionalization of the channel or structure of the molecular sieves under microwave irradiation have been reported as well/801... 

MTBE synthesis from /-butanol and methanol in a membrane reactor has been reported by Salomon et al. [2.453]. Hydrophilic zeolite membranes (mordenite or NaA) were employed to selectively remove water from the reaction atmosphere during the gas-phase synthesis of MTBE. This reaction was carried out over a bed of Amberlyst 15 catalyst packed in the inside of a zeolite tubular membrane. Prior to reaction, the zeolite membranes were characterized by measuring their performance in the separation of the equilibrium mixture containing water, methanol, /-butanol, MTBE, and isobutene. The results obtained with zeolite membrane reactors were compared with those of a fixed-bed reactor (FBR) under the same operating conditions. MTBE yields obtained with the PBMR at 334 K reached 67.6 %, under conditions, where the equilibrium value without product removal (FBR) would be 60.9%. 

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. 

Li X, Kita H, Zhu H, Zhang Z, Tanaka K. Synthesis of longterm acid-stable zeolite membranes and their potential application to esterification reactions. J Membr Sci 2009 339(1-2) 224-223. 

The application of permeable composite monolith membranes for the FT synthesis has been tested [122]. An overview of concepts associated with this reactor type has been presented (Figure 12.25) [123]. Novel uses of this concept have been advanced, and some experimental results have demonstrated the ability to operate at high CO conversion with metal FT catalysts by removal of the water produced during the synthesis [ 124] and the encapsulation of an FT catalyst by a zeolite membrane layer to effect upgrading reactions in the FT reactor [125]. The potential of this technique merits further studies to evaluate the ability to scale to a commercial level. 

Synthesis of membranes with high permeability and selectivity, that is, oriented and thin zeolite membranes. Optimal MR operation requires the membrane flux to be in balance with the reaction rate. A large number of factors - such as the support, organic additives, temperature, and profile - have a significant influence on the microstructure and overall quality of the membrane. However, the precise correlation between the synthesis procedure and conditions and the properties of the resultant zeolite membranes is not clear. In contrast, the majority of membranes synthesized so far are MFI-type zeolite membranes that have pore diameters 5 A, which are still too big to separate selectively small gaseous molecules. Zeolite membranes with pores in the 3 A range should be developed for membrane reactors, to separate small gas molecules on the basis of size exclusion. In addition, a method to produce zeolite membranes without non-zeolite pores or defects has to be found. 

---