Zeolite membrane reactors synthesis

This chapter gives an overview of the synthesis procedures and appUcations of zeoUte membranes (gas separation, pervaporation, zeolite-membrane reactors), as well as new emerging appUcations in the micro- and nanotechnology field. Related areas such as new zeoUte and zeoUte-related materials for membranes, alternative supports, and scale-up issues are also discussed. 

Nevertheless, the development of zeolite-membrane reactors still requires improvements in the fluxes and separation factors attained to date, an objective to which many efforts have been devoted in recent years with the aim of materializing an industrial application of zeolite-membrane reactors. Several reviews have been published in the last 5 years dealing completely or partially with zeolite membranes [2,3,5,161,162,165-167]. Particularly, noteworthy have been the advances regarding the use of supports of different natures and characteristics (see Section 10.6.4), the control of the orientation and thickness of zeolite layers (see Section 10.2.1.2), and the preparation of new zeolite materials such as membranes (see Section 10.3). In spite of these advances, before zeolite-membrane reactors are used in industry (see Section 10.6.5), signihcant progress must be achieved in more prosaic issues such as scale-up and control of the synthesis process to increase membrane reproducibility. 

Salomon MA, Coronas J, Menendez M, and Santamarfa J. Synthesis of MTBE in zeolite membrane reactors. Appl Catal A Gen 2000 200 201-210. 

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 series of original synthesis strategies has been also reported recently such as flow-through reactors for the homogeneous synthesis of zeolite membranes [77], centrifugal force field [114] or electrophoresis [115] for the preparation of A-type membranes, and pulse laser deposition (PLD) for the secondary growth of oriented MCM-22 membranes [116]. 

Kiatkittipong et al. (2002) investigated a PV membrane reactor for the synthesis of ethyl icri-butyl ether (ETBE) from a liquid phase reaction between EtOH and TEA. Supported p-zeolite and PVA membrane were used as catalyst and as membrane in the reactor, respectively. The permeation studies of water-EtOH binary system revealed that the membrane worked effectively for water removal for the mixtures containing water lower than 62 mol%. The permeation studies of quaternary mixtures (water-EtOH-TBA-ETBE) were performed at three temperature levels of 323, 333, and 343 K. It was found that the manbrane was preferentially permeable to water. 

Figure 12.25 Membrane reactors for FT synthesis from the literature (a) distributed feeding of reactants A and B, (b) in situ water removal by selective membrane (F, feed S, sweep), (cl) plug-through contactor membrane (PCM) with wide transport pores, (c2) forced-through flow membrane contactor, product and heat removal by circulated liquid product, (d) zeolite encapsulated FT catalyst, P, modified product [123].

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. 

Zeolite membranes have attracted a lot of interest for their uniform pore size at molecular scale, which allows the separation of liquid and gaseous mixtures in a continuous way. Because of their thermal and chemical stability, they can also be used in processes at high temperatures and in the presence of organic solvents where polymeric membranes fail. In addition, zeolite materials exhibit intrinsic catalytic properties which clearly suggests the use of zeolite membranes as catalytic membrane reactors (CMRs). In the last two decades, enormous progress on zeolite membrane synthesis has been made, but only 20 structures are used for membrane preparation even if 170 zeolitic structures are available today (Baerlocher et al, 2007). The high cost and poor reproducibility in the synthesis step hinder the application of the zeolite membranes at industrial level (Caro et al, 2005 Mcleary et al., 2006). Until now, only NaA and T-type zeolite membranes... 

Researchers have made enormous efforts and significant progress in understanding the synthesis procedures and the formation mechanism of the zeolite layer in order to improve the quality of the membranes. However, further improvements based on producing reproducible defect-free zeolite membranes and to reduce their manufacturing cost need to be carried out to facilitate their introduction in the industry as membrane reactors. 

The past decade has seen significant advances in the ability to synthesize different types of microporous coatings with ordered structures from a wide range of different precursors. Sol-gel hydrothermal synthesis is one of the most promising methods for obtaining zeolitic coatings (films and membranes) on the internal surface of channels of catalytic microstructured reactors. Zeolite[Pg.277]

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