Reverse osmosis solute preferential sorption

It is to this topic of solute preferential sorption in reverse osmosis that this paper is dedicated. Specifically, this discussion will involve a description of solute preferential sorption, an overview of the literature in the area, and finally a presentation of some recent work on the removal of aromatic hydrocarbons from water. The significance of this work is at least two-fold. From a practical point of view the classes of solutes which demonstrate preferential attraction to the membrane material tend to be organic compounds and the removal and recovery of these solutes from water is environmentally and economically important. From a theoretical point of view an understanding of the phenomena involved is essential to the achievement of a fundamental description of the RO process. Although this paper deals solely with aqueous solutions and cellulose acetate membranes, it Is important to recognize that the concepts discussed can be extended to Include other membrane materials and non-aqueous systems. 

The advantage of the preferential sorption-capillary flow approach to reverse osmosis lies in its emphasis on the mechanism of separation at a molecular level. This knowledge is useful when it becomes necessary to predict membrane performance for unknown systems. Also, the approach is not restricted to the so-called "perfect", defect-free membranes, but encompasses the whole range of membrane pore size. Until recently, the application of a quantitative model to the case of solute preferential sorption has been missing. Attempts to change this situation have been made by Matsuura and Sourirajan (21) by using a modified finely porous model. In addition to the usual features of this model (9-12), a Lennard-Jones type of potential function is Incorporated to describe the membrane-solute interaction. This model is discussed elsewhere in this book. 

In conclusion, several Important points of this work should be reiterated. An understanding and quantitative description of solute preferential sorption Is Imperative to the advancement of a fundamental knowledge of the separation mechanism and to the application of reverse osmosis. For the systems studied,... 

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... 

Figure 1. Schematic of preferential sorption-capillary flow mechanism for reverse-osmosis separations of sodium chloride from aqueous solutions...

According to the above mechanism, reverse osmosis separation is governed by two distinct factors, namely (i) an equilibrium effect which is concerned with the details of preferential sorption in the vicinity of the membrane surface, and (ii) a kinetic effect which is concerned with the mobilities of solute and solvent through membrane pores. While the former (equilibrium effect) is governed by repulsive and attractive potential gradients in the vicinity of the membrane surface, the latter (mobility effect) is governed both by the potential gradients (equilibrium effect) and the steric effects associated with the structure and size of molecules relative to those of pores on the membrane surface. 

The preferential sorption-capillary flow mechanism of reverse osmosis does that. In the NaCl-H20-cellulose acetate membrane system, water is preferentially sorbed at the membrane-solution Interface due to electrostatic repulsion of ions in the vicinity of materials of low dielectric constant (13) and also due to the polar character of the cellulose acetate membrane material. In the p-chlorophenol-water-cellulose acetate membrane system, solute is preferentially sorbed at the interface due to higher acidity (proton donating ability) of p-chlorophenol compared to that of water and the net proton acceptor (basic) character of the polar part of cellulose acetate membrane material. In the benzene-water-cellulose acetate membrane, and cumene-water-cellulose acetate membrane systems, again solute is preferentially sorbed at the interface due to nonpolar... 

Preferential Sorption at Membrane-Solution Interfaces and Solute Separation In Reverse Osmosis... 

With particular reference to reverse osmosis systems involving cellulose acetate membranes and aqueous solutions, the membrane material has both polar and nonpolar character, and the solvent, of course, is polar. When these two components of the reverse osmosis system are kept constant, preferential sorption at the membrane-solution interface, and, in turn, solute separation in reverse osmosis, may be expected to be controlled by the chemical nature of the solute. If the latter can be expressed by appropriate quantitative physicochemical parameters representing polar-, steric-, nonpolar-, and/or ionic-character of the solutes, then one can expect unique correlations to exist between such parameters and reverse osmosis data on solute separations for each membrane. Experimental results confirm that such is indeed the case (18). 

Gibbs adsorption equation is an expression of the natural phenomenon that surface forces can give rise to concentration gradients at Interfaces. Such concentration gradient at a membrane-solution Interface constitutes preferential sorption of one of the constituents of the solution at the interface. By letting the preferentially sorbed Interfacial fluid under the Influence of surface forces, flow out under pressure through suitably created pores in an appropriate membrane material, a new and versatile physicochemical separation process unfolds itself. That was how "reverse osmosis" was conceived in 1956. 

In the performance data of various polyamide and related membranes published to date there should be valuable information for molecular design of more excellent barrier materials. But at present a means for their evaluation and optimization is still not clear. One of the reasons may at least come from the competitive flood of proposals for the detailed mechanisms of reverse osmosis, e.g. the solution-diffusion model, the sieve model, the preferential sorption model and so on. 109)... 

A number of models have been developed over the years to describe reverse osmosis. These models Include the solution-diffusion model, the finely porous model, and the preferential sorption - capillary flow model. In each case, the model was originally developed based on the separation of aqueous,salt solutions. The application of each of these models to systems which exhibit anomalous behavior will be discussed in this section. 

Another concept of water and salt transport in reverse osmosis is the preferential sorption-capillary flow mechanism. In this model, the surface of a membrane is microporous and heterogeneous at all levels of solute separation. It is hypothesized that, due to the chemical nature of the membrane skin layer in contact with the aqueous solution, a preferential sorption for the water causes a sorbed water layer to be formed at the skin. This layer of purified water is then forced through the capillary pores by pressure. 

Several mechanisms have been proposed to explain reverse osmosis. According to the preferential sorption-capillary flow mechanism of Sourirajan [114], reverse osmosis separation is the combined result of an interfacial phenomenon and fluid transport under pressure through capillary pores. Figure 5.58a is a conceptual model of this mechanism for recovery of fresh water from aqueous salt solutions. The surface of the membrane in contact with the solution has a preferential sorption for water and/or preferential repulsion for the solute, while a continuous removal of the preferentially sorbed interfacial water, which is of a monomolecular nature, is effected by flow under pressure through the membrane capillaries. According to this model, the critical pore diameter for a maximum separation and permeability is equal to twice the thickness of the preferentially sorbed interfacial layer (Figure 5.58b). 

The preferential sorption-capillary flow model starts from the consideration of the solid-liquid interface. For example, aqueous sodium chloride solution is in contact with a solid surface. Sodium chloride solution represents the reverse osmosis system where the separation of solute (sodium chloride) flrom solvent (water) occurs. This system also represents one of the most important applications of reverse osmosis, i.e., seawater desalination. A concentration gradient should inevitably appear at the solution-solid interface, as shown in Figure 6.1. The Gibbs adsorption isotherm... 

In its most general sense, reverse osmosis describes any pressure-driven process that depends on preferential diffusion of a liquid through a membrane that is selectively permeable to the liquid. Illustrated in Figures 5.5 and 5.6, reverse osmosis is a very useful and well-developed technique for the purification of water. Basically, it consists of forcing pure water through a semipermeable membrane that allows the passage of water but not of other material. This process, which is not simply sieve separation or ultrafiltration, depends on the preferential sorption of water on the surface of a porous cellulose acetate or polyamide membrane. Pure water from the sorbed layer is forced through pores in the membrane under pressure. If the thickness of the sorbed water layer is d, the pore diameter for optimum separation should be 2d. The optimum pore diameter depends on the thickness of the sorbed pure water layer and may be several times the diameters of the solute and solvent molecules. 

Surface adsorption potential Vapor pressure of a liquid, volatility of a solute Water removed by vaporization from a solution or moist solid Water removed from a solid by sublimation excess aonimulation of a species at the interface of phase 1 and phase 2 gas-solid, liquid-solid different volatilities of bulk liquids and solutes evaporation of water sublimation of water adsorption, chromatography (gas-solid, liquid-solid) (Table 1, Sections 3.3.7.G, 4.1.5) distillation, stripping (Table 1, Sections 4.1.1, 4.1.2) evaporation, drying (Table 1) freeze-drying (Table 1) gas separation by surface diffusion (Section S.4.2.4), preferential sorption and capillary transport in reverse osmosis (Table 2) pervaporation (Table 2, Section 6.3.3.4) (plus membrane permeability) membrane distillation (Song et ai, 2008) ... 

There are a number of other models of transport of solvent and solute through a reverse osmosis membrane the Kedem-Katchalsky model, the Spiegler-Kedem model, the frictional model, the finely porous model, the preferential sorption-capUlary flow model, etc. Most of these models have heen reviewed and compared in great detail hy Soltanieh and GiU (1981). We will restrict ourselves in this hook to the solution-diffusion and solution-diffusion-imperfection flux expressions for a number of reasons. First, the form of the solution-diffusion equation is most commonly used and is also functionally equivalent to the preferential sorption-capiUary flow model. Secondly, the solution-diffusion-imperfection model is functionally representative of a number of more exact three-transport-coefficient models, even though the transport coefficients in this model are concentration-dependent... 

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