Reverse osmosis membrane separation

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). 

Conditions sometimes exist that may make separations by distillation difficult or impractical or may require special techniques. Natural products such as petroleum or products derived from vegetable or animal matter are mixtures of very many chemically unidentified substances. Thermal instability sometimes is a problem. In other cases, vapor-liquid phase equilibria are unfavorable. It is true that distillations have been practiced successfully in some natural product industries, notably petroleum, long before a scientific basis was established, but the designs based on empirical rules are being improved by modern calculation techniques. Even unfavorable vapor-liquid equilibria sometimes can be ameliorated by changes of operating conditions or by chemical additives. Still, it must be recognized that there may be superior separation techniques in some cases, for instance, crystallization, liquid-liquid extraction, supercritical extraction, foam fractionation, dialysis, reverse osmosis, membrane separation, and others. The special distillations exemplified in this section are petroleum, azeotropic, extractive, and molecular distillations. 

Goosen, M.F.A., Sablani, S., Del-Cin, M. Wilf, M. (2011) Effect of cyclic changes in temperature and pressure on permeation properties of composite polyamide spiral wound reverse osmosis membranes. Separation Science and Technology, 46 (1), 14-26. 

Today, various treatment techniques and processes have been used to remove the metallic ions from the wastewater, including precipitation, evaporation, solvent extraction, ion exchange, reverse osmosis, membrane separation, and so on. Most of these methods suffer from some drawbacks such as high capital and operational costs for the treatment and disposal of the residual metal sludge [32-34]. Therefore, efforts are made to develop low-cost materials to remove contaminants from aqueous solutions. Fortunately, recent development of nanotechnique has shed a light on this field. Nanoparticles, often characterized by a significant amount of surfaces, have been attracting much interest because of their unique properties and potential applications. 

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. 

Cellulose acetate Loeb-Sourirajan reverse osmosis membranes were introduced commercially in the 1960s. Since then, many other polymers have been made into asymmetric membranes in attempts to improve membrane properties. In the reverse osmosis area, these attempts have had limited success, the only significant example being Du Font s polyamide membrane. For gas separation and ultrafUtration, a number of membranes with useful properties have been made. However, the early work on asymmetric membranes has spawned numerous other techniques in which a microporous membrane is used as a support to carry another thin, dense separating layer. 

In reverse osmosis membranes, the pores are so smaH, in the range 0.5— 2 nm in diameter, that they ate within the range of the thermal motion of the polymer chains. The most widely accepted theory of reverse osmosis transport considers the membrane to have no permanent pores at aH. Reverse osmosis membranes are used to separate dissolved microsolutes, such as salt, from water. The principal appHcation of reverse osmosis is the production of drinking water from brackish groundwater or seawater. Figure 25 shows the range of appHcabHity of reverse osmosis, ultrafiltration, microfiltration, and conventional filtration. 

Reverse Osmosis. This was the first membrane-based separation process to be commercialized on a significant scale. The breakthrough discovery that made reverse osmosis (qv) possible was the development of the Loeb-Sourirajan asymmetric cellulose acetate membrane. This membrane made desalination by reverse osmosis practical within a few years commercial plants were installed. The total worldwide market for reverse osmosis membrane modules is about 200 million /yr, spHt approximately between 25% hoUow-ftber and 75% spiral-wound modules. The general trend of the industry is toward spiral-wound modules for this appHcation, and the market share of the hoUow-ftber products is gradually falling (72). 

Reverse Osmosis. Membranes are used for the separation of smaller components (<500 daltons). They have smaller pore space and are tighter than those used for ultrafiltration. High pressure pumps, usually of the positive piston or multistage centrifugal type, provide pressures up to 4.14 MPa (600 psi). 

Transport Models. Many mechanistic and mathematical models have been proposed to describe reverse osmosis membranes. Some of these descriptions rely on relatively simple concepts others are far more complex and require sophisticated solution techniques. Models that adequately describe the performance of RO membranes are important to the design of RO processes. Models that predict separation characteristics also minimize the number of experiments that must be performed to describe a particular system. Excellent reviews of membrane transport models and mechanisms are available (9,14,25-29). 

M. Williams, "Measurement and Mathematical Description of Separation Characteristics of Ha2ardous Organic Compounds with Reverse Osmosis Membranes," dissertation. University of Kentucky, Lexiagton, Ky., 1993. 

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. 

The most important application of semi-permeable membranes is in separations based on reverse osmosis. These membranes generally have pores smaller than 1 nm. The pressure across the semi-permeable membranes for reverse osmosis is generally much larger than those for ultrafiltration, for example. This is because reverse osmosis is usually used for small molecules which have a much higher osmotic pressure, because of the higher number density, than the colloids separated in ultrafiltration. As a result reverse osmosis membranes have to be much more robust than ultrafiltration membranes. Since the focus of our discussion in this chapter will be on reverse osmosis based separations, we will describe these membranes in greater detail. 

Asymmetric membranes have a tight, low-permeability, retentive zone that performs the desired separation and a more open, high-permeability zone that provides mechanical strength to the overall membrane. This structure is particularly critical to the economic viability of reverse-osmosis membranes. Asymmetric membranes operated in TFF mode must have the tight side facing the feed channel so that particles are retained on its surface and can be acted upon by the tangential flow. Asymmetric membranes operated in NFF mode can... 

Reverse osmosis" is the popular name of a general process for the separation of substances in solution. The process consists in letting the solution flow under pressure through an appropriate porous membrane (called the "reverse osmosis membrane") and withdrawing the membrane permeated product generally at atmospheric pressure and surrounding temperature. 

Reverse osmosis is applicable for the separation, concentration, and/or fractionation of inorganic or organic substances in aqueous or nonaqueous solutions in the liquid or the gaseous phase, and hence it opens a new and versatile field of separation technology in chemical process engineering. Many reverse osmosis processes are also popularly called "ultrafiltration", and many reverse osmosis membranes are also practically useful as ultrafilters. 

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... 

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