Nanofiltration structure

Membrane Porosity Separation membranes run a gamut of porosity (see Fig. 22-48). Polymeric and metallic gas separation membranes, electrodialysis membranes, pervaporation membranes, and reverse osmosis membranes are nonporous, although there is hnger-ing controversy over the nonporosity of the latter. Porous membranes are used for microfiltration and ultrafiltratiou. Nanofiltration membranes are probably charged porous structures. 

In the search to develop new materials for immobilization of homogeneous transition metal catalyst to facilitate catalyst-product separation and catalyst recychng, the study of dendrimers and hyperbranched polymers for application in catalysis has become a subject of intense research in the last five years [68], because they have excellent solubility and a high number of easily accessible active sites. Moreover, the pseudo-spherical structure with nanometer dimensions opens the possibility of separation and recycling by nanofiltration methods. Although dendrimers allow for controlled incorporation of transition metal catalysts in the core [69] as well as at the surface [70], a serious drawback of this approach is the tedious preparation of functionalized dendrimers by multi-step synthesis. 

Dendritic catalysts can be recycled by using techniques similar to those applied with their monomeric analogues, such as precipitation, two-phase catalysis, and immobilization on insoluble supports. Furthermore, the large size and the globular structure of the dendrimer can be utilized to facilitate catalyst-product separation by means of nanofiltration. Nanofiltration can be performed batch wise or in a continuous-flow membrane reactor (CFMR). The latter offers significant advantages the conditions such as reactant concentrations and reactant residence time can be controlled accurately. These advantages are especially important in reactions in which the product can react further with the catalytically active center to form side products. 

There are reports of numerous examples of dendritic transition metal catalysts incorporating various dendritic backbones functionalized at various locations. Dendritic effects in catalysis include increased or decreased activity, selectivity, and stability. It is clear from the contributions of many research groups that dendrimers are suitable supports for recyclable transition metal catalysts. Separation and/or recycle of the catalysts are possible with these functionalized dendrimers for example, separation results from precipitation of the dendrimer from the product liquid two-phase catalysis allows separation and recycle of the catalyst when the products and catalyst are concentrated in two immiscible liquid phases and immobilization of the dendrimer in an insoluble support (such as crosslinked polystyrene or silica) allows use of a fixed-bed reactor holding the catalyst and excluding it from the product stream. Furthermore, the large size and the globular structure of the dendrimers enable efficient separation by nanofiltration techniques. Nanofiltration can be performed either batch wise or in a continuous-flow membrane reactor (CFMR). 

Metal oxides, used for manufacturing of ceramic nanofiltration membranes, are intrinsically hydrophilic. This limits the use of these membranes to polar solvents filtration of nonpolar solvents (n-hexane, toluene, cyclohexane) usually yields zero fluxes. Attempts have been made to modify the pore structure by adding hydrophobic groups, for example, in a silane coupling reaction [38, 43]. This approach is similar to modifications of ultrafiltration and microfiltration membranes... 

Due to recent advances in membrane development, nanofiltration membranes are nowadays increasingly used for applications in organic solvents [27, 58]. This narrows the gap between pervaporation and nanofiltration. It is even possible that the requirements for membrane structures completely overlap for the two processes whereas membrane stability becomes more important for nanofiltration membranes, the performance of pervaporation membranes could be improved by using an optimized (thinner) structure for the top layers. It might even be possible to use the same membranes in both applications. At this moment it is not possible to define which membrane structure is necessary for nanofiltration or for pervaporation, and which membrane is expected to have a good performance in nanofiltration, in pervaporation or in both. Whereas pervaporation membranes are dense, nanofiltration membranes... 

Polymeric membranes with a less porous structure, pervaporation membranes as well as nanofiltration membranes, can be described by a solution-diffusion mecha-... 

Nanofiltration (NF) and RO are closely related in that both share the same composite membrane structure and are generally used to remove ions from solution. However, NF membranes use both size and charge of the ion to remove it from solution whereas RO membranes rely only on "solution-diffusion" transport to affect a separation (see Chapters 16.2 and 4.1, respectively). Nanofiltration membranes have pore sizes ranging from about 0.001 to 0.01 microns, and therefore,... 

Besides the use of homogeneously soluble polymethacrylates or poylstyrene, as for the examples described above, other soluble supports may be used in order to yield a catalyst which can be retained by ultra- or nanofiltration membranes. Several groups have introduced catalysts (chiral and nonchiral) coupled to dendrimers and dendrimer-like structures [54, 59-76]. Compared with catalysts coupled to polymers, such complexes offer the advantage of a more defined structure. Thus, the number of active sites can be controlled more accurately. As these will be present at the surface of a globular structure they will be easily accessible. 

The main characteristics of nanofiltration membranes made of oxide ceramics is that they exhibit a microporous structure with charged pore walls depending on pH and ionic strength of feed solutions. Three main cases are distinguished in the discussion of mechanisms involved in permeation and separation processes using microporous ceramic nanofilters ... 

As a general conclusion to this part dedicated to nanofiltration with ceramic membranes one can assume that the general behaviour of these membranes can be assimilated to the behaviour of electrically charged organic nanofiltration membranes. However some specificities exist with ceramic nanofilters due to a sintered metal oxide grains derived porous structure and an amphoteric character... 

Whereas the pore-flow mechanism describes transport through porous UF, NF and RO membranes show a transient structure between porous and non-porous, with probably also sorption-diffusion as part of the transport mechanism. Nanofiltration is a relatively new membrane process with a nominal MWCO in the range of 200-1000 Da. Its application in water treatment has been growing rapidly, but the nonaqu-eous application is still an emerging field. All efforts to enlarge catalysts become superfluous when the membranes are capable of retaining off-the-shelf TMCs. 

The use of nanofiltration membranes as supporting membranes have been also reported [28]. In this case, direct filtration of ionic liquids through the nanofiltration membrane was not possible at a gas pressure up to 7 bars. The ionic liquids with cations associated with straight or branched hydrocarbon chains were easily absorbed into the polymeric membrane allowing the nanoporous structure saturated with the ionic liquids. 

This chapter focuses on the chemical processing of ceramic membranes, which has to date constituted the major part of inorganic membrane development. Before going further into the ceramic aspect, it is important to understand the requirements for ceramic membrane materials in terms of porous structure, chemical composition, and shape. In separation technologies based on permselective membranes, the difference in filtered species ranges from micrometer-sized particles to nanometer-sized species, such as molecular solutes or gas molecules. One can see that the connected porosity of the membrane must be adapted to the class of products to be separated. For this reason, ceramic membrane manufacture is concerned with macropores above 0.1 pm in diameter for microfiltration, mesopores ranging from 0.1 pm to 2 nm for ultrafiltration, and nanopores less than 2 nm in diameter for nanofiltration, per-vaporation, or gas separation. Dense membranes are also of interest for gas... 

---