Reverse osmosis membranes barrier layer

Mitrovic and Knezic (1979) also prepared ultrafiltration and reverse osmosis membranes by this technique. Their membranes were etched in 5% oxalic acid. The membranes had pores of the order of 100 nm, but only about 1.5 nm in the residual barrier layer (layer AB in Figure 2.15). The pores in the barrier layer were unstable in water and the permeability decreased during the experiments. Complete dehydration of alumina or phase transformation to a-alumina was necessary to stabilize the pore structure. The resulting membranes were found unsuitable for reverse osmosis but suitable for ultrafiltration after removing the barrier layer. Beside reverse osmosis and ultrafiltration measurements, some gas permeability data have also been reported on this type of membranes (Itaya et al. 1984). The water flux through a 50/im thick membrane is about 0.2mL/cm -h with a N2 flow about 6cmVcm -min-bar. The gas transport through the membrane was due to Knudsen diffusion mechanism, which is inversely proportional to the square root of molecular mass. 

The origin of thin-film-composite reverse osmosis membranes began with a newly formed research institute and one of its first employees, Peter S. Francis. North Star Research and Development Institute was formed in Minneapolis during 1963 to fill a need for a nonprofit contract research institute in the Upper Midwest. Francis was given the mission of developing the chemistry division through support, in part, by federal research contracts. At this time the Initial discoveries by Reid and Breton ( ) on the desalination capability of dense cellulose acetate membranes and by Loeb and Sourlrajan (,2) on asymmetric cellulose acetate membranes had recently been published. Francis speculated that improved membrane performance could be achieved, if the ultrathin, dense barrier layer and the porous substructure of the asymmetric... 

The thin film composite membrane exhibited superior overall rejection performance in these tests, with ammonia and nitrate rejection showing an outstanding improvement. It has also been reported that silica rejection by the thin film composite membranes is superior to that of cellulose acetate. While the above data indicates a marginal improvement in the rejection of chemical oxygen demand (COD), which is an indication of organic content, other tests conducted by membrane manufacturers show that the polyurea and polyamide membrane barrier layers exhibit an organic rejection that is clearly superior to that of cellulose acetate. Reverse osmosis element manufacturers should be contacted for rejection data on specific organic compounds. ... 

Reverse osmosis membrane is produced in sheet form-up to 60 inches wide and lengths up to 1,500 feet-and as a hollow fine fiber. The asymmetric cellulose acetate was originally produced as a sheet and later as a hollow fine fiber. The asymmetric aromatic polyamide was originally produced as a hollow fine fiber and later in sheet form. The composite membranes with polyamide or polyurea membrane barrier layers are produced in sheet form as of the end of 1987, but research has been and will continue to be done to produce the composite reverse osmosis membranes as a hollow fine fiber. 

Chlorine has been added to the feedwater upstream of reverse osmosis pretreatment. However, since chlorine will depolymerize the polyurea membrane barrier layer in the spiral wound element, with subsequent loss of desalination properties, the chlorine is removed in the pretreatment system dechlorination basin. This removal is chemically accomplished by the addition of sodium bisulfite. The chlorine level in the influent and effluent to the dechlorination basin is continuously monitored. The feedwater is then transferred from the dechlorination basin to the cartridge filter feed pumping station by gravity flow and it is then pumped to the cartridge filters. 

A thin film composite reverse osmosis membrane can be defined as a multilayer membrane in which an ultrathin semipermeable membrane layer is deposited on a preformed, finely microporous support structure. This contrasts with asymmetric reverse osmosis membranes in which both the barrier layer and the porous substructure are formed in a single-step phase inversion process and are integrally bonded. 

Fabrication of a thin film composite membrane is typically a more expensive route to reverse osmosis membranes because it involves a two-step process versus the one-step nature of the phase inversion film casting method. However, it offers the possibility of each individual layer being tailor-made for maximum performance. The semipermeable coating can be optimized for water flux and solute rejection characteristics. The microporous sublayer can be optimized for porosity, compression resistance and strength. Both layers can be optimized for chemical resistance. In nearly all thin film composite reverse osmosis membranes, the chemical composition of the surface barrier layer is radically different from the chemical composition of the microporous sublayer. This is a common result of the thin film composite approach. 

The term "thin film composite" has the connotation that the barrier layer is extremely thin, and hence quite fragile. Indeed, the barrier layer may be quite thin, varying to as low as 200 angstroms depending on the nature of the particular reverse osmosis membrane and its method of manufacture. But this does not necessarily result in fragility. Some of these membranes may be considerably... 

Figure 5.12 Topside and underside of the FT-30 composite reverse osmosis membrane (a) topside showing well-developed ridge-and-valley structure, and also an area of membrane barrier layer folded over upon itself (b) underside of the barrier layer (foldover zone) showing the network of micropores inside the ridge-and-valley structure.

Water flux through reverse osmosis membranes is considerably dependent on the hydrophilic character of the barrier layer. In the composite membrane approach, highly hydrophilic barrier layer compositions can be used, suitably insolubilized by crosslinking. To a large extent, water flux and salt rejection can be controlled by the type and extent of crosslinking. 

In the market of reverse osmosis membrane today, thin film composite membranes have gotten a major position for their outstanding membrane performance and durability. In the usual thin film composite membrane, an ultra-thin salt barrier layer, formed by an in-situ inter cial polymerization reaction, covers the surface of a porous polysulfone substrate. Figure 1 illustrates a typical structure of the thin film composite membrane, TORAY "UTC-70". 

An RO membrane acts as a barrier to flow, allowing selective passage of a particular species (solvent) while other species (solutes) are retained partially or completely. Solute separation and permeate solvent (water in most cases) flux depend on the material selection, the preparation procedures, and the structure of the membrane barrier layer [5,15]. Cellulose acetate (CA) is the material for the first generation reverse osmosis membrane. The announcement of CA membranes for sea water desalination by Loeb and Sourirajan in 1960 triggered the applications of membrane separation processes in many industrial sectors. CA membranes are prepared by the dry-wet phase inversion technique. Another polymeric material for RO is aromatic polyamide [16]. 

The above equation indicates that the selectivity of the composite membrane is controlled by a barrier component whose resistance is far greater than the other. This is the principle underlying the development of the composite reverse osmosis membrane where an active surface layer is supported by a porous support layer (Figure 5.7). The resistance to the permeant flow is contributed almost... 

This membrane demonstrated a vastly improved flux compared with the poly(piperazine isophthalamide) membrane, but its seawater salt rejection was low — in the range of 60 to 70 percent. A reverse osmosis test with a magnesium sulfate feedwater showed greater than 99 percent salt retention, however, dispelling the possibility that low sodium chloride rejections were due to defects in the polyamide barrier layer. The piperazine polyamide was soon concluded to have the following structure (see Reaction 111). 

Concentration polarization can dominate the transmembrane flux in UF, and this can be described by boundary-layer models. Because the fluxes through nonporous barriers are lower than in UF, polarization effects are less important in reverse osmosis (RO), nanofiltration (NF), pervaporation (PV), electrodialysis (ED) or carrier-mediated separation. Interactions between substances in the feed and the membrane surface (adsorption, fouling) may also significantly influence the separation performance fouling is especially strong with aqueous feeds. 

In the petroleum industry, dewaxing solvents are separated by ultrafiltration from dewaxed oils by chemically resistant membranes made from polysulfone or polyimide. In a related process, pentane is separated from deasphalted heavy oil under conditions intermediate between reverse osmosis and ultrafilttation (ca. 15 bar applied pressure). High-molecular-weight hydrocarbons in the oil form a gel layer on the surface of a polysulfone support membrane. This gel restricts passage of heavier hydrocarbons but not pentane, which is recovered as permeate. To separate other hydrocarbon mixtures that do not contain gel-forming components, polymeric additives would be used as a rejecting barrier substitute. 

In the case of a composite membrane consisting of a skinless porous substrate and a dense film, permeability and permselectivity may be determined solely by the resistance of the denser film. Different membrane polymers may therefore be employed for the thin barrier layer and the thick support structure. This permits a combination of properties which are not available in a single material. Such membranes were initially developed for desalination by reverse osmosis where they are known as thin- or ultrathin-film composites or nonlntegrally-skinned membranes. A second type of composite membrane is utilized for gas separations. It is a composite consisting of an integrally-skinned or asymmetric membrane coated by a second, more permeable skin which is used to fill skin defects. The inventors of the latter have entitled their device a resfstanee model membrane, but the present author prefers the term coated integrally-skinned composites. 

Properties of FT-30. The properties of FT-30 membranes have been reviewed in several publications. Therefore, only the salient features that relate to the chemistry of the barrier layer will be considered here. Reverse osmosis performance of FT-30 under seawater and brackish water test conditions was described by Cadotte et al (48) and by Larson et al (51). In commercially produced spiral-wound elements the FT-30 membrane typically gives 99.0 to 99.2 percent salt rejection at 24 gfd (40 L/sq m/hr) flux in seawater reverse osmosis tests with 3.5 percent synthetic seawater at 800 psi (5516 kPascaJJand 25°C. 

A concentration boundary layer theory clearly is needed to relate C to C, so that membrane properties such as L, a, and P can be correlated with R, at various operating conditions. Slso, since ir in Equations 1 and 5 is an independently determined function of C, a boundary ayer theory could correlate the observed filtrate velocity, J (averaged along the fiber length), with average applied pressure AP. For sufficiently high axial flow velocities, C == C, and a major theoretical barrier to data analysis is removeS. Some early work in reverse osmosis ( ) was done with flat-sheet membranes and large feed stream velocities. 

Membranes are used for a wide variety of separations. A membrane serves as a barrier to some particles while allowing others to selectively pass through. The pore size, shape, and electrostatic surface charge are fundamental to particle removal. Synthetic polymers (cellulose acetate, polyamides, etc.) and inorganic materials (ceramics, metals) are generally the principal materials of construction. Membranes may be formed with symmetric or asymmetric pores, or formed as composites of ultra thin layers attached to coarser support material. Reverse osmosis, nanofiltration, ultrafiltration, and microfiltration relate to separation of ions, macromolecules, and particles in the 0.001 to 10 pm range (Rushton et al. 1996). 

The properties of FT-30 membranes have been reviewed in several publications, including reverse osmosis performance under seawater and brackish water test conditions.60"62 In commercially produced spiral-wound elements, the FT-30 membrane typically gives 99.1 to 99.3% salt rejection at 24 gfd flux in seawater desalination at 800 psi and 25°C. In brackish water applications, FT-30 spiral elements can be operated at system pressures of as low as 225 psi while producing water at 22 to 24 gfd. Similar flux levels are possible with the TFC-202 and LP-300 membranes, as mentioned earlier. But it is notable that those membranes achieve such high fluxes through use of extremely thin surface barrier layers about only one-tenth the thickness of the FT-30 barrier layer. 

Second, insoluble crosslinked barrier layer compositions are possible, and, in fact, are almost universal in the composite membrane approach. Optimum reverse osmosis performance and chemical stability can be achieved, in part, due to preparation of crosslinked compositions. This is readily possible by the composite membrane approach, but not so simple by the asymmetric membrane approach. The PA-300, FT-30, and PEC-1000 barrier layer compositions, for example, are simply not feasible to prepare by asymmetric film casting techniques. The composite approach, therefore, is far more versatile. 

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