Reverse osmosis membrane selectivity

The seminal discovery that transformed membrane separation from a laboratory to an industrial process was the development, in the early 1960s, of the Loeb-Sourirajan process for making defect-free, high flux, asymmetric reverse osmosis membranes (5). These membranes consist of an ultrathin, selective surface film on a microporous support, which provides the mechanical strength. The flux of the first Loeb-Sourirajan reverse osmosis membrane was 10 times higher than that of any membrane then avaUable and made reverse osmosis practical. The work of Loeb and Sourirajan, and the timely infusion of large sums of research doUars from the U.S. Department of Interior, Office of Saline Water (OSW), resulted in the commercialization of reverse osmosis (qv) and was a primary factor in the development of ultrafiltration (qv) and microfiltration. The development of electro dialysis was also aided by OSW funding. 

Membranes made by interfacial polymerization have a dense, highly cross-linked interfacial polymer layer formed on the surface of the support membrane at the interface of the two solutions. A less cross-linked, more permeable hydrogel layer forms under this surface layer and fills the pores of the support membrane. Because the dense cross-linked polymer layer can only form at the interface, it is extremely thin, on the order of 0.1 p.m or less, and the permeation flux is high. Because the polymer is highly cross-linked, its selectivity is also high. The first reverse osmosis membranes made this way were 5—10 times less salt-permeable than the best membranes with comparable water fluxes made by other techniques. 

Reverse osmosis membrane separations are governed by the properties of the membrane used in the process. These properties depend on the chemical nature of the membrane material, which is almost always a polymer, as well as its physical stmcture. Properties for the ideal RO membrane include low cost, resistance to chemical and microbial attack, mechanical and stmctural stabiHty over long operating periods and wide temperature ranges, and the desired separation characteristics for each particular system. However, few membranes satisfy all these criteria and so compromises must be made to select the best RO membrane available for each appHcation. Excellent discussions of RO membrane materials, preparation methods, and stmctures are available (8,13,16-21). 

A reverse osmosis membrane acts as the semipermeable barrier to flow ia the RO process, aHowiag selective passage of a particular species, usually water, while partially or completely retaining other species, ie, solutes such as salts. Chemical potential gradients across the membrane provide the driving forces for solute and solvent transport across the membrane. The solute chemical potential gradient, —is usually expressed ia terms of concentration the water (solvent) chemical potential gradient, —Afi, is usually expressed ia terms of pressure difference across the membrane. 

Membranes. Photopolymer chemistry is being applied to the design and manufacture of a variety of membrane materials. In these applications, photopolymer technology is used to precisely define the microscopic openings in the membrane as it is being formed or to modify an existing membrane. Some of the applications of photopolymer chemistry to membranes include the modification of ultrafiltration membranes (78) and the manufacture of amphiphilic (79), gas permeable (80), untrafiltration (81), ion-selective electrode (82) and reverse osmosis membranes. 

This implies that the selective layer of reverse osmosis membranes may have a different origin from that of the micelles. Such a case is clearly identified by examination of the skin structure of cellulose acetate/poly(bromophenylene oxide phosphonate) alloy membranes (1 ), which exhibit a high flux and high salt separation (Figure 13). The skin rests on an assembly of giant spheres (up to 1 pm in diameter) and is certainly originated by a different coagulation mechanism than that of the spheres. 

This paper has provided the reader with an introduction to a class of polymers that show great potential as reverse osmosis membrane materials — poly(aryl ethers). Resistance to degradation and hydrolysis as well as resistance to stress Induced creep make membranes of these polymers particularly attractive. It has been demonstrated that through sulfonation the hydrophilic/hydrophobic, flux/separation, and structural stability characteristics of these membranes can be altered to suit the specific application. It has been Illustrated that the nature of the counter-ion of the sulfonation plays a role in determining performance characteristics. In the preliminary studies reported here, one particular poly(aryl ether) has been studied — the sulfonated derivative of Blsphenol A - polysulfone. This polymer was selected to serve as a model for the development of experimental techniques as well as to permit the investigation of variables... 

Albany International Research Co. has developed an advanced hollow fiber composite reverse osmosis membrane and module under the name of Quantro II . This composite membrane is comprised of a porous hollow fiber substrate on which has been deposited a rejection barrier capable of fluxes of commercial importance at high rejection of dissolved salts at elevated temperatures. Resistance to active chlorine has been demonstrated. Proprietary processes have been developed for spinning of the fiber, establishment of the rejection barrier and processing of the fiber to prepare modules of commercial size. Prototype modules are currently in field trials against brackish and seawater feed solutions. Applications under consideration for this membrane include brackish and seawater desalination as well as selected industrial concentration processes. 

Equation (2.37) is simplified by assuming that the membrane selectivity is high, that is, DiK jl DjKj/ . This is a good assumption for most of the reverse osmosis membranes used to separate salts from water. Consider the water flux first. At the point at which the applied hydrostatic pressure balances the water activity gradient, that is, the point of osmotic equilibrium in Figure 2.6(b), the flux of water across the membrane is zero. Equation (2.37) becomes... 

The most extensive studies of plasma-polymerized membranes were performed in the 1970s and early 1980s by Yasuda, who tried to develop high-performance reverse osmosis membranes by depositing plasma films onto microporous poly-sulfone films [60,61]. More recently other workers have studied the gas permeability of plasma-polymerized films. For example, Stancell and Spencer [62] were able to obtain a gas separation plasma membrane with a hydrogen/methane selectivity of almost 300, and Kawakami et al. [63] have reported plasma membranes... 

Depending on the enrichment term (E0) of the membrane, the modulus can be larger or smaller than 1.0. For reverse osmosis E0 is less than 1.0, and the concentration polarization modulus is normally between 1.1 and 1.5 that is, the concentration of salt at the membrane surface is 1.1 to 1.5 times larger than it would be in the absence of concentration polarization. The salt leakage through the membrane and the osmotic pressure that must be overcome to produce a flow of water are increased proportionately. Fortunately, modem reverse osmosis membranes are extremely selective and permeable, and can still produce useful desalted water under these conditions. In other membrane processes, such as pervaporation or ultrafiltration, the concentration polarization modulus may be as large as 5 to 10 or as small as 0.2 to 0.1, and may seriously affect the performance of the membrane. 

Equation (4.9) shows that concentration polarization increases exponentially as the total volume flow Jv through the membrane increases. This is one of the reasons why modem spiral-wound reverse osmosis membrane modules are operated at low pressures. Modem membranes have two to five times the water permeability, at equivalent salt selectivities, of the first-generation cellulose acetate reverse osmosis membranes. If membrane modules containing these new membranes were operated at the same pressures as early cellulose acetate modules, two to five times the desalted water throughput could be achieved with the same... 

Many nanofiltration membranes follow these rules, but oftentimes the behavior is more complex. Nanofiltration membranes frequently combine both size and Donnan exclusion effects to minimize the rejection of all salts and solutes. These so-called low-pressure reverse osmosis membranes have very high rejections and high permeances of salt at low salt concentrations, but lose their selectivity at salt concentrations above 1000 or 2000 ppm salt in the feed water. The membranes are therefore used to remove low levels of salt from already relatively clean water. The membranes are usually operated at very low pressures of 50-200 psig. 

Reverse osmosis membranes can be divided into subclasses according to their solute/water selectivity and operating pressure regimes. Figure 30 shows a number of commercial membranes developed for seawater and brackish desalination, and for nanofiltration. These include cellulose ester and polyamide asymmetric membranes available since the 1960s, and high-performance composite membranes developed in the 1970s. Collectively, they make it possible to produce potable water from virtually all saline water sources. 

Microporous membranes can be used in a manner similar to reverse osmosis to selectively allow small solute molecules and/or solvents to pass through the membrane and to prevent large dissolved molecules and suspended solids from passing through. Microfiltration refers to the retention of molecules typically in the size range from 0.05 to 10 pm. Ultrafiltration refers to the range from 1 to 100 nm. To retain even smaller molecules, reverse osmosis, sometimes called hyperfiltration, can be used down to less than 2 nm. 

Much effort has been expended in attempting to use membranes for separations. Reverse osmosis membranes are used worldwide for water purification. These membranes are based on size selectivity depending on the pores used. They do not have the ability to selectively separate target species other than by size. Incorporation of carrier molecules into liquid membrane systems of various types has resulted in achievement of highly selective separations on a laboratory scale. Reviews of the extensive literature on the use of liquid membrane systems for carrier-mediated ion separations have been published [15-20]. A variety of liquid membranes has been studied including bulk (BLM), emulsion (ELM), thin sheet supported (TSSLM), hollow fiber supported (HFSLM), and two module hollow fiber supported (TMHFSLM) types. Of these liquid membranes, only the ELM and TMHFSLM types are likely to be commercialized. Inadequacies of the remaining... 

The deposition of a plasma polymer on an appropriate porous substrate to form a composite reverse osmosis membrane is a typical example of the second case. In both cases, however, the selection of the substrate membrane is the crucially important factor, particularly in the second case. In the application of nanofilm, the pore size of the substrate membrane must have the uniformity of pore size in nanometer scale, which is an extremely difficult requirement. 

Reverse osmosis Reliability Selectivity Cost Increment improvements in membrane and process design will gradually reduce costs... 

Summary of Physicochemical Parameters. In the previous section steric parameters 4 . and were introduced to describe the effective size of solution components and the average size of the transport corridor, respectively. A variety of quantities that could be used to represent

dense membranes and the skin layer of reverse osmosis membranes in which the transport corridors are beyond the resolution capabilities of modern instruments and may be dynamic in nature. Therefore, any discussion of membrane material selection based on steric considerations must be qualitative. 

The latest major innovation, and also economically the most successful breakthrough, was achieved by Henis and Tripodl (34-38) with their invention of the resistance model (RM) fiber membranes in late 1979. In agreement with the history of reverse osmosis membrane development, they selected a high-strength, glassy polymer as membrane material, such as polysulfone with a glass transition... 

The development of composite reverse osmosis membranes is reviewed with emphasis on those types that have survived the selection for commercial development. 

These advantages are reflected in the intense activity in filing patents on composite reverse osmosis membranes, and in the growing selection of commercially available types. Because of these advantages, many new examples of such membranes are likely to reach commercial status in the future, whereas very few new asymmetric membranes can be anticipated. 

Meiny different supports have been used to prepare ILMs Including cellulose acetate reverse osmosis membranes (1 6, 25, 29, ), micro-porous polypropylene ultrafiltration membranes (31-3 T7 polyvinyl chloride filters (35), and hollow fiber cellulose acetate reverse osmosis membranes T36). Way et al. ( ) discuss the chemical and physical properties that must be considered when an ILM support Is selected. 

Finally, we selected TAB and m-phenylenediamine (MPD) as the polyamine and TPC and TMC as the polyacylchloride. In consequence, we developed and commercialized "UTC-70" (Figure 4), a reverse osmosis membrane for ultrapure water production in electronics industries. Moreover, we found changing composition of these materials set us free to design membrane performance. 

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