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Zeolite membrane

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Zeolite membrane

A zeolite membrane is a synthetic membrane made of crystalline aluminosilicate materials, typically aluminum, silicon, and oxygen with positive counterions such as Na+ and Ca2+ within the structure. Zeolite membranes serve as a low energy separation method. They have recently drawn interest due to their high chemical and thermal stability, and their high selectivity. Currently zeolites have seen applications in gas separation, membrane reactors, water desalination, and solid state batteries. Currently zeolite membranes have yet to be widely implemented commercially due to key issues including low flux, high cost of production, and defects in the crystal structure.

There are several methods used for the formation of Zeolite membranes.

The In Situ method involves Zeolite membranes being formed on microporous supports of various materials, typically aluminum oxide or stainless steel. These supports are then immersed in a solution of Aluminum and Silicon at a specific stoichiometric ratio. Other factors of this solution can affect the formation of the zeolite membrane including: pH, Ionic Strength, temperature, and the addition of structure-determining reagents . Upon heating the solution, the crystals of the membrane begin to grow on the supports.

In 2012, a “seeding method” was developed to produce zeolite membranes. In this case, the support is seeded with preformed zeolite crystals, before immersing it in the solution. These crystals allow for the formation of thinner membranes that typically contain fewer defects by growing the membranes off of existing structures.

Zeolite membranes drew initial interest as a separation method due to their high thermal and chemical stabilities. The crystal structure of zeolite membranes also creates a uniform pore size of approximately .3-1.3 nm in diameter. The crystal structure of zeolites also leads to the presence of several defects, which can often create gaps in the structure larger than these pores. The presence of defects can make these membranes far less effective, and it is difficult to produce defect free zeolite membranes.

There are several mechanisms of transport that govern the separation of molecules by zeolite membranes. The main mechanisms for separation by zeolite membranes are molecular sieving, diffusion, and adsorption. Molecular sieving involves the rejection of any molecules of a size greater than the pore size of the membrane. This is a relatively simple sieving process which can separate very large molecules. Adsorption involves molecules passing through the pores of the membrane being adsorbed onto the membrane surface. Adsorption properties of the membranes can be changed by adjusting various structural properties of the membrane.

Surface diffusion is a process in which molecules adsorb to the pore wall of the membrane, and are slowly transported through the pores. During surface diffusion, molecules that are adsorbed at a higher rate can begin to block the membrane pores from other, less adsorbed, molecules. Surface diffusion can account for the high selectivity of certain molecules such as hydrogen by zeolite membranes. Surface diffusion typically plays a larger role in the transport of molecules at lower temperatures.

Knudsen diffusion also contributes to the varying selectivity of zeolite membranes towards different molecules. Knudsen diffusion takes place when molecules are momentarily adsorbed to the pore wall and are then reflected off the surface in a random direction. This random motion allows for separation of molecules based on their velocities. Graham's law for diffusion dictates that lighter molecules will have a higher average velocity than heavier molecules, thus resulting in an increased flux with respect to lighter molecules. These differences in flux can be used to separate different molecules using zeolite membranes.

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