RO membrane

Sales of RO membrane products were as high as 118 million aimually in the late 1980s, and continued growth is expected (10). 

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). 

Most commercially available RO membranes fall into one of two categories asymmetric membranes containing one polymer, or thin-fHm composite membranes consisting of two or more polymer layers. Asymmetric RO membranes have a thin ( 100 nm) permselective skin layer supported on a more porous sublayer of the same polymer. The dense skin layer determines the fluxes and selectivities of these membranes whereas the porous sublayer serves only as a mechanical support for the skin layer and has Httle effect on the membrane separation properties. Asymmetric membranes are most commonly formed by a phase inversion (polymer precipitation) process (16). In this process, a polymer solution is precipitated into a polymer-rich soHd phase that forms the membrane and a polymer-poor Hquid phase that forms the membrane pores or void spaces. 

Measurable Process Parameters. The RO process is relatively simple ia design. It consists of a feed water source, feed pretreatment, high pressure pump, RO membrane modules, and ia some cases, post-treatment steps. A schematic of the RO process is shown ia Figure 2a. 

The three streams and associated variables of the RO membrane process are shown in Figure 2b the feed the product stream, called the permeate and the concentrated reject stream, called the concentrate or retentate. The water flow through the membrane is reported in terms of water flux, J. ... 

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). 

Reverse osmosis models can be divided into three types irreversible thermodynamics models, such as Kedem-Katchalsky and Spiegler-Kedem models nonporous or homogeneous membrane models, such as the solution—diffusion (SD), solution—diffusion—imperfection, and extended solution—diffusion models and pore models, such as the finely porous, preferential sorption—capillary flow, and surface force—pore flow models. Charged RO membrane theories can be used to describe nanofiltration membranes, which are often negatively charged. Models such as Dorman exclusion and the... 

A fundamental difference exists between the assumptions of the homogeneous and porous membrane models. For the homogeneous models, it is assumed that the membrane is nonporous, that is, transport takes place between the interstitial spaces of the polymer chains or polymer nodules, usually by diffusion. For the porous models, it is assumed that transport takes place through pores that mn the length of the membrane barrier layer. As a result, transport can occur by both diffusion and convection through the pores. Whereas both conceptual models have had some success in predicting RO separations, the question of whether an RO membrane is truly homogeneous, ie, has no pores, or is porous, is still a point of debate. No available technique can definitively answer this question. Two models, one nonporous and diffusion-based, the other pore-based, are discussed herein. 

Solution—Diffusion Model. In the solution—diffusion model, it is assumed that (/) the RO membrane has a homogeneous, nonporous surface layer (2) both the solute and solvent dissolve in this layer and then each diffuses across it (J) solute and solvent diffusion is uncoupled and each is the result of the particular material s chemical potential gradient across the membrane and (4) the gradients are the result of concentration and pressure differences across the membrane (26,30). The driving force for water transport is primarily a result of the net transmembrane pressure difference and can be represented by equation 5 ... 

Equation 7 shows that as AP — oo, P — 1. The principal advantage of the solution—diffusion (SD) model is that only two parameters are needed to characterize the membrane system. As a result, this model has been widely appHed to both inorganic salt and organic solute systems. However, it has been indicated (26) that the SD model is limited to membranes having low water content. Also, for many RO membranes and solutes, particularly organics, the SD model does not adequately describe water or solute flux (27). Possible causes for these deviations include imperfections in the membrane barrier layer, pore flow (convection effects), and solute—solvent—membrane interactions. 

A = 4.05 X lO " cm/(s-kPa)(4.1 X 10 cm/(s-atm)) and = 1.3 x 10 cm/s (4)//= 1 mPa-s(=cP), NaCl diffusivity in water = 1.6 x 10 cm /s, and solution density = 1 g/cm . Figure 4 shows typical results of this type of simulation of salt water permeation through an RO membrane. Increasing the Reynolds number in Figure 4a decreases the effect of concentration polarization. The effect of feed flow rate on NaCl rejection is shown in Figure 4b. Because the intrinsic rejection, R = 1 — Cp / defined in terms of the wall concentration, theoretically R should be independent of the Reynolds... 

Factors affecting RO membrane separations and water flux include feed variables such as solute concentration, temperature, pH, and pretreatment requirements membrane variables such as polymer type, module geometry, and module arrangement and process variables such as feed flow rate, operating time and pressure, and water recovery. 

There has been considerable research on chlorine-resistant RO membranes (48—52). A poly(/n j -2,5 dimethyl)pipera2inthiofura2anainide used in the presence of low (3 mg/L) concentrations of chlorine resulted in a membrane life of three years (48). A copolyamide hoUow-fiber membrane for use in desalination has been developed that is resistant to 0.5 mg/L chlorine (49). Millipore Corporation has also developed a sulfonated polysulfone member that has desirable chlorine-resistance properties. 

The effects of small halocarbons, such as chloroform, bromoform, and carbon tetrachloride, on several RO membranes have been considered (61). 

RO membrane FT30-BW. Compounds are in dilute aqueous solution. Pressure = 1.3-2.0 MPa (13—20 atm). 

Reverse osmosis processes for desalination were first appHed to brackish water, which has a lower I DS concentration than seawater. Brackish water has less than 10,000 mg/L IDS seawater contains greater than 30,000 mg/L IDS. This difference in IDS translates into a substantial difference in osmotic pressure and thus the RO operating pressure required to achieve separation. The need to process feed streams containing larger amounts of dissolved soHds led to the development of RO membranes capable of operating at pressures approaching 10.3 MFa (1500 psi). Desalination plants around the world process both brackish water and seawater (15). 

RO membrane modules are available from many manufacturers including, for hoUow-fiber modules, DuPont and Dow/FUmTec Corporation, and for spinal-wound modules, UOP Inc., Millipore Corporation, Nitto-Denko America, Inc., Toray Industries Inc., Dow/FUmTec Corporation, and DuPont. 

The basic approximate equation for the separation process gives the water flux, m" (kg/m /s) across an RO membrane, in the absence of fouling,... 

Typically, 95% of dissolved salts are removed from the brine. All particulates are removed. However, due to their molecular porosity, RO membranes do not remove dissolved gases, such as CI2, CO2, and O2. 

Basic Principles of Operation RO and NF are pressure-driven processes where the solvent is forced through the membrane by pressure, and the undesired coproducts frequently pass through the membrane by diffusion. The major processes are rate processes, and the relative rates of solvent and sohite passage determine the quality of the product. The general consensus is that the solution-diffusion mechanism describes the fundamental mechanism of RO membranes, but a minority disagrees. Fortunately, the equations presented below describe the obseiwed phenomena and predict experimental outcomes regardless of mechanism. 

The second major membrane type is a composite. Starting with a loose asymmetric membrane, usually a UF membrane, a coating is applied which is polymerized in situ to become the salt rejecflng membrane. This process is used for most high-performance flat-sheet RO membranes, as well as for many commercial nanofiltration membranes. The chemistry of the leading RO membranes is known, but... 

Membrane Characterization Membranes are always rated for flux and rejection. NaCl is always used as one measure of rejection, and for a veiy good RO membrane, it will be 99.7 percent or more. Nanofiltration membranes are also tested on a larger solute, commonly MgS04. Test results are veiy much a function of how the test is run, and membrane suppliers are usually specific on the test conditions. Salt concentration will be specified as some average of feed and exit concentration, but both are bulk values. Salt concentration at the membrane governs performance. Flux, pressure, membrane geome-tiy, and cross-flow velocity all influence polarization and the other variables shown in Fig. 22-63. 

Folding is defined in Background and Definitions and is a significant problem in most process applications, and somewhat of a problem in most water applications. RO membranes may be fouled by sparingly soluble sealants which supersaturate at the membrane. 

Chlorine Tolerance Most of the best RO membranes are attacked by oxidants, and they are particularly susceptible to chlorine. A particularly sensitive locus for attack is the amidic hydrogen. Cellu-losic membranes are generally less sensitive, and pass the chlorine into the permeate giving downstream biocidal activity, veiy useful for under-the-sink RO. These factors are largely responsible for CA s survival in RO membranes. Chlorine, whatever its vices, has the virtue of being a known, effective, residual bactericide and a good inhibitor of... 

Ultrafiltration may be distinguished from other membrane operations by example When reverse osmosis is used to process whey, it passes only the water and some of the lactic acid (due to the solubihty of lactic acid in RO membranes). Nanofiltration used on whey will pass most of the sodium salts while retaining the calcium salts and most of the lactose. Microfiltration will pass everything except the particulates and the bacteria. 

---