Reverse osmosis flux

When pressurized liquid is used lo separate micrometer-size particles from fluids, the process is called microfiltration. Generally particle sizes are front 0.02 to 10 pm. Thus compared lo ultrafiltration and reverse osmosis, fluxes and pore sizes are large, osmotic pressure low. and pressures moderate. Two types of niicrofiltration processes exist, crossflow and deadend. Commercially, the former is growing at Ihe expense of the latter. 

The final parameter in Equation (4.9) that determines the value of the concentration polarization modulus is the diffusion coefficient A of the solute away from the membrane surface. The size of the solute diffusion coefficient explains why concentration polarization is a greater factor in ultrafiltration than in reverse osmosis. Ultrafiltration membrane fluxes are usually higher than reverse osmosis fluxes, but the difference between the values of the diffusion coefficients of the retained solutes is more important. In reverse osmosis the solutes are dissolved salts, whereas in ultrafiltration the solutes are colloids and macromolecules. The diffusion coefficients of these high-molecular-weight components are about 100 times smaller than those of salts. 

Membrane distillation offers a number of advantages over alternative pressure-driven processes such as reverse osmosis. Because the process is driven by temperature gradients, low-grade waste heat can be used and expensive high-pressure pumps are not required. Membrane fluxes are comparable to reverse osmosis fluxes, so membrane areas are not excessive. Finally, the process is still effective with slightly reduced fluxes even for very concentrated solutions. This is an advantage over reverse osmosis, in which the feed solution osmotic pressure places a practical limit on the concentration of a salt in the feed solution to be processed. 

One can actually consider the trapped solution morphology as a functional definition of the asymmetric membranes. It should be emphasized that this viewpoint clearly differentiates asymmetric membranes that have shown the highest reverse osmosis fluxes from membranes with a thin dense layer of normal solid morphology. 

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. 

Nonporous Dense Membranes. Nonporous, dense membranes consist of a dense film through which permeants are transported by diffusion under the driving force of a pressure, concentration, or electrical potential gradient. The separation of various components of a solution is related directiy to their relative transport rate within the membrane, which is determined by their diffusivity and solubiUty ia the membrane material. An important property of nonporous, dense membranes is that even permeants of similar size may be separated when their concentration ia the membrane material (ie, their solubiUty) differs significantly. Most gas separation, pervaporation, and reverse osmosis membranes use dense membranes to perform the separation. However, these membranes usually have an asymmetric stmcture to improve the flux. 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

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. 

Interfacial polymerization membranes are less appHcable to gas separation because of the water swollen hydrogel that fills the pores of the support membrane. In reverse osmosis, this layer is highly water swollen and offers Httle resistance to water flow, but when the membrane is dried and used in gas separations the gel becomes a rigid glass with very low gas permeabiUty. This glassy polymer fills the membrane pores and, as a result, defect-free interfacial composite membranes usually have low gas fluxes, although their selectivities can be good. 

The performance of reverse osmosis membranes is generaUy described by the water and salt fluxes (74,75). The water flux,/ is linked to the pressure and concentration gradients across the membrane by equation 4 ... 

The salt flux, across a reverse osmosis membrane can be described by equation 5 where is a constant and and < 2 the salt concentration differences across the membrane. 

Some data iEustrating the effect of pressure on the water and salt fluxes and the salt rejection of a good quaUty reverse osmosis membrane are shown ia Figure 34 (76). 

Fig. 34. Water and salt fluxes through a high performance reverse osmosis membrane, when tested with a 3.5% NaCl feed solution. The water flux increases, whereas the salt flux is essentially independent of appHed pressure (76). To convert MPa to psig, multiply by 145.

The pressure to be used for reverse osmosis depends on the salinity of the feedwater, the type of membrane, and the desired product purity. It ranges from about 1.5 MPa for low feed concentrations or high flux membranes, through 2.5—4 MPa for brackish waters, and to 6—8.4 MPa for seawater desalination. In desalination of brackish or sea water, typical product water fluxes through spiral-wound membranes are about 600—800 kg/m /d at a recovery ratio RR of 15% and an average salt rejection of 99.5%, where... 

Equations (22-86) and (22-89) are the turbulent- and laminar-flow flux equations for the pressure-independent portion of the ultrafiltra-tion operating curve. They assume complete retention of solute. Appropriate values of diffusivity and kinematic viscosity are rarely known, so an a priori solution of the equations isn t usually possible. Interpolation, extrapolation, even precuction of an operating cui ve may be done from limited data. For turbulent flow over an unfouled membrane of a solution containing no particulates, the exponent on Q is usually 0.8. Fouhng reduces the exponent and particulates can increase the exponent to a value as high as 2. These equations also apply to some cases of reverse osmosis and microfiltration. In the former, the constancy of may not be assumed, and in the latter, D is usually enhanced very significantly by the action of materials not in true solution. 

Kev>erse Osmosis (RO) Membranes A type of membrane system for treating oily wastewater is currently undergoing commercialization by Bend Research, Inc. The system uses a tube-side feed module that yields high fluxes while being able to handle high-sohds-content waste streams (Ref. 25). Another type of reverse osmosis technique is being designed to yield ultrapurified HF recovered from... 

Irreversible thermodynamics has also been used sometimes to explain reverse osmosis [14,15]. If it can be assumed that the thermodynamic forces responsible for reverse osmosis are sufficiently small, then a linear relationship will exist between the forces and the fluxes in the system, with the coefficients of proportionality then referred to as the phenomenological coefficients. These coefficients are generally notoriously difficult to obtain, although some progress has been made recently using approaches such as cell models [15]. 

In reverse osmosis water is forced by pressure through a very fine-pore membrane, which has the property of rejecting dissolved salts. The process thus removes both particulate and dissolved matter. Generally, the flux of water is extremely slow, so that large membrane areas have to be installed to achieve the desired output. Different grades of membrane show different rejections and fluxes. 

A phenomenon that is particularly important in the design of reverse osmosis units is that of concentration polarization. This occurs on the feed-side (concentrated side) of the reverse osmosis membrane. Because the solute cannot permeate through the membrane, the concentration of the solute in the liquid adjacent to the surface of the membrane is greater than that in the bulk of the fluid. This difference causes mass transfer of solute by diffusion from the membrane surface back to the bulk liquid. The rate of diffusion back into the bulk fluid depends on the mass transfer coefficient for the boundary layer on feed-side. Concentration polarization is the ratio of the solute concentration at the membrane surface to the solute concentration in the bulk stream. Concentration polarization causes the flux of solvent to decrease since the osmotic pressure increases as the boundary layer concentration increases and the overall driving force (AP - An) decreases. 

Membrane processes such as ultrahltrahon or reverse osmosis have been proposed as oil removal processes. Laboratory tests have indicated favorable oil removal, although relatively low flux rates, membrane fouling, and membrane life problems have presented concerns for the practical applicahon of membrane processes to oil removal. 

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. 

It was recognized by both. the Florida and UCLA groups that economic utilization of reverse osmosis depended on obtaining a great increase in flux(and water oermeation constant) without serious loss in electrolyte rejection properties. It was also recognized that one path to increased flux lay in decreased membrane thickness. 

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