Concentration polarization ultrafiltration

Cowman, L.M. and Ethier, C.R., Concentration and concentration gradient measurements in an ultrafiltration concentration polarization layer. Part I A laser-based refractometric experimental technique. Journal of Membrane Science 131 1997 95-105. 

Screening Equipment Filtration Cake Filters Centrifugal Filters Principles of Cake Filtration Clarifying Filters Liquid Clarification Gas Cleaning Principles of Clarification Crossflow Filtration Types of Membranes Permeate Flux for Ultrafiltration Concentration Polarization Partial Rejection of Solutes Microfiltration... 

Figure 4.4. Ultrafiltration—concentration polarization and microgel. As dilute sol circulates over membrane, sol is concentrated at membrane surface, and particles diffuse back to dilute region. Microgel does not diffuse, remains at membrane.

Fig. 23. Two types of hollow-fiber modules used for gas separation, reverse osmosis, and ultrafiltration applications, (a) Shell-side feed modules are generally used for high pressure appHcations up to - 7 MPa (1000 psig). Fouling on the feed side of the membrane can be a problem with this design, and pretreatment of the feed stream to remove particulates is required, (b) Bore-side feed modules are generally used for medium pressure feed streams up to - 1 MPa (150 psig), where good flow control to minimise fouling and concentration polarization on the feed side of the membrane is desired.

A key factor determining the performance of ultrafiltration membranes is concentration polarization due to macromolecules retained at the membrane surface. In ultrafiltration, both solvent and macromolecules are carried to the membrane surface by the solution permeating the membrane. Because only the solvent and small solutes permeate the membrane, macromolecular solutes accumulate at the membrane surface. The rate at which the rejected macromolecules can diffuse away from the membrane surface into the bulk solution is relatively low. This means that the concentration of macromolecules at the surface can increase to the point that a gel layer of rejected macromolecules forms on the membrane surface, becoming a secondary barrier to flow through the membrane. In most ultrafiltration appHcations this secondary barrier is the principal resistance to flow through the membrane and dominates the membrane performance. 

Dynamic membranes are concentration—polarization layers formed in situ from the ultrafiltration of coUoidal material analogous to a precoat in conventional filter operations. Hydrous zirconia has been thoroughly investigated other materials include bentonite, poly(acryhc acid), and films deposited from the materials to be separated (18). 

P. Dejmek, "PermeabiHty of the Concentration Polarization Layer in Ultrafiltration of Macro Molecules," Proceedings of the International Symposium, Separation Processes by Membranes, Paris, Mar. 13—14,1975. 

Concentration Polarization The equations governing cross-flow mass transfer are developed in the section describing ultrafiltration. 

Figure 10.13 shows a typical batch ultrafiltration setup. As the solution is pumped through the filter unit, the permeate is collected and the retentate is recycled. The volume of the solution reduces with time and the solute concentration increases. Develop a correlation for the time required to reduce the solution volume from V0 to V. Assume that the concentration polarization is negligible. Also assume that the membrane totally rejects the solute. 

Two other major factors determining module selection are concentration polarization control and resistance to fouling. Concentration polarization control is a particularly important issue in liquid separations such as reverse osmosis and ultrafiltration. In gas separation applications, concentration polarization is more easily controlled but is still a problem with high-flux, highly selective membranes. Hollow fine fiber modules are notoriously prone to fouling and concentration polarization and can be used in reverse osmosis applications only when extensive, costly feed solution pretreatment removes all particulates. These fibers cannot be used in ultrafiltration applications at all. 

The layer of solution immediately adjacent to the membrane surface becomes depleted in the permeating solute on the feed side of the membrane and enriched in this component on the permeate side. Equivalent gradients also form for the other component. This concentration polarization reduces the permeating component s concentration difference across the membrane, thereby lowering its flux and the membrane selectivity. The importance of concentration polarization depends on the membrane separation process. Concentration polarization can significantly affect membrane performance in reverse osmosis, but it is usually well controlled in industrial systems. On the other hand, membrane performance in ultrafiltration, electrodialysis, and some pervaporation processes is seriously affected by concentration polarization. 

Figure 4.1 shows the concentration gradients that form on either side of a dialysis membrane. However, dialysis differs from most membrane processes in that the volume flow across the membrane is usually small. In processes such as reverse osmosis, ultrafiltration, and gas separation, the volume flow through the membrane from the feed to the permeate side is significant. As a result the permeate concentration is typically determined by the ratio of the fluxes of the components that permeate the membrane. In these processes concentration polarization gradients form only on the feed side of the membrane, as shown in Figure 4.3. This simplifies the description of the phenomenon. The few membrane processes in which a fluid is used to sweep the permeate side of the membrane,...

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. 

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. 

The effect of concentration polarization on specific membrane processes is discussed in the individual application chapters. However, a brief comparison of the magnitude of concentration polarization is given in Table 4.1 for processes involving liquid feed solutions. The key simplifying assumption is that the boundary layer thickness is 20 p.m for all processes. This boundary layer thickness is typical of values calculated for separation of solutions with spiral-wound modules in reverse osmosis, pervaporation, and ultrafiltration. Tubular, plate-and-ffame, and bore-side feed hollow fiber modules, because of their better flow velocities, generally have lower calculated boundary layer thicknesses. Hollow fiber modules with shell-side feed generally have larger calculated boundary layer thicknesses because of their poor fluid flow patterns. 

Figure 4.11 shows that ultrafiltration and pervaporation for the removal of organic solutes from water are both seriously affected by concentration polarization. In ultrafiltration, the low diffusion coefficient of macromolecules produces a concentration of retained solutes 70 times the bulk solution volume at the membrane surface. At these high concentrations, macromolecules precipitate, forming a gel layer at the membrane surface and reducing flux. The effect of this gel layer on ultrafiltration membrane performance is discussed in Chapter 6. 

In the discussion of concentration polarization to this point, the assumption is made that the volume flux through the membrane is large, so the concentration on the permeate side of the membrane is determined by the ratio of the component fluxes. This assumption is almost always true for liquid separation processes, such as ultrafiltration or reverse osmosis, but must be modified in a few gas separation and pervaporation processes. In these processes, a lateral flow of gas is sometimes used to change the composition of the gas on the permeate side of the membrane. Figure 4.14 illustrates a laboratory gas permeation experiment using this effect. As the pressurized feed gas mixture is passed over the membrane surface, certain components permeate the membrane. On the permeate side of the membrane, a lateral flow of helium or other inert gas sweeps the permeate from the membrane surface. In the absence of the sweep gas, the composition of the gas mixture on the permeate side of the membrane is determined by the flow of components from the feed. If a large flow of sweep gas is used, the partial... 

Figure 6.6 Illustration of the formation of a gel layer of colloidal material on the surface of an ultrafiltration membrane by concentration polarization...

The effect of the gel layer on the flux through an ultrafiltration membrane at different feed pressures is illustrated in Figure 6.7. At a very low pressure p, the flux Jv is low, so the effect of concentration polarization is small, and a gel layer does not form on the membrane surface. The flux is close to the pure water flux of the membrane at the same pressure. As the applied pressure is increased to pressure p2, the higher flux causes increased concentration polarization, and the concentration of retained material at the membrane surface increases. If the pressure is increased further to p3, concentration polarization becomes enough for the retained solutes at the membrane surface to reach the gel concentration cgel and form the secondary barrier layer. This is the limiting flux for the membrane. Further increases in pressure only increase the thickness of the gel layer, not the flux. 

Concentration polarization can also interfere with the ability of an ultrafiltration membrane to fractionate a mixture of dissolved macromolecules. Figure 6.13 [8] shows the results of experiments with a membrane with a molecular weight... 

The need to control concentration polarization and membrane fouling dominates the design of ultrafiltration modules. The first commercially successful... 

For treating water containing VOCs with separation factors of more than 500, for which concentration polarization is a serious problem, feed-and-bleed systems similar to those described in the chapter on ultrafiltration can be used. For small feed volumes a batch process as illustrated in Figure 9.16 is more suitable. In a batch system, feed solution is accumulated in a surge tank. A portion of this solution is then transferred to the feed tank and circulated at high velocity through the pervaporation modules until the VOC concentration reaches the desired level. At this time, the treated water is removed from the feed tank, the tank is loaded with a new batch of untreated solution, and the cycle is repeated. 

During reverse osmosis and ultrafiltration membrane concentration, polarization and fouling are the phenomena responsible for limiting the permeate flux during a cyclic operation (i.e., permeation followed by cleaning). That is, membrane lifetimes and permeate (i.e., pure water) fluxes are primarily affected by the phenomena of concentration polarization (i.e., solute build up) and fouling (e.g., microbial adhesion, gel layer formation, and solute adhesion) at the membrane surface [11]. 

Many models have been published to calculate the microfiltration process. One important factor is the concentration polarization, which represents the most important limiting physical obstacle. At high particle concentration and with time, a layer is formed on the membrane. This layer is responsible for the flux reduction. A comprehensive overview on this technique is given by Ripperger52 and Staude.53 Often similar or identical module types are used in microfiltration and ultrafiltration. 

---