Membrane processes pervaporation

The pervaporation feed coming from the distillation unit contains no impurities and no pretreatment is necessary in this case. System design for per aporation differs from that of other membrane processes. Pervaporation is the only process where a phase transition... 

The most convenient mathematical method of describing pervaporation is to divide the overall separation processes into two steps, as shown in Figure 40. The first is evaporation of the feed Hquid to form a (hypothetical) saturated vapor phase on the feed side of the membrane. The second is permeation of this vapor through the membrane to the low pressure permeate side of the membrane. Although no evaporation actually takes place on the feed side of the membrane during pervaporation, this approach is mathematically simple and is thermodynamically completely equivalent to the physical process. The evaporation step from the feed hquid to the saturated vapor phase produces a separation, which can be defined (eq. 13) as the ratio of... 

So, Sulfolane and Carom, ca 1997, are two current rival processes. Sulfolane has a slight advantage over Carom ia energy consumption, while Carom has 6—8% less capital for the same capacity Sulfolane unit. In 1995, Exxon (37) commercialized the most recent technology for aromatics recovery when it used copolymer hoUow-fiber membrane ia concentration-driven processes, pervaporation and perstraction, for aromatic—paraffin separation. Once the non aromatic paraffins and cycloparaffins are removed, fractionation to separate the C to C aromatics is relatively simple. 

The most common membrane systems are driven by pressure. The essence of a pressure-driven membrane process is to selectively permeate one or more species through the membrane. The stream retained at the high pressure side is called the retentate while that transported to the low pressure side is denoted by the permeate (Fig. 11.1). Pressure-driven membrane systems include microfiltration, ultrafiltration, reverse osmosis, pervaporation and gas/vapor permeation. Table ll.l summarizes the main features and applications of these systems. 

When ionic liquids are used as replacements for organic solvents in processes with nonvolatile products, downstream processing may become complicated. This may apply to many biotransformations in which the better selectivity of the biocatalyst is used to transform more complex molecules. In such cases, product isolation can be achieved by, for example, extraction with supercritical CO2 [50]. Recently, membrane processes such as pervaporation and nanofiltration have been used. The use of pervaporation for less volatile compounds such as phenylethanol has been reported by Crespo and co-workers [51]. We have developed a separation process based on nanofiltration [52, 53] which is especially well suited for isolation of nonvolatile compounds such as carbohydrates or charged compounds. It may also be used for easy recovery and/or purification of ionic liquids. 

An survey of recent developments in membrane processes, involving reverse osmosis (RO), ultrafiltration (UF), microfiltration (MF), electrodialysis (ED), dialysis (D), pervaporation (Pr), gas permeation (GP), and emulsion liquid membrane (ELM), has been provided by Sirkar (1997). 

Aroma compounds are often heat sensitive and their purification by membrane processes, which work at near ambient conditions, can be attractive. Alternatively, when pervaporation is used then temperatures can be kept low. A variety of aroma substances from aqueous solutions have been recovered. Baudot and Marin (1997) and Baudot et al. (1999) have made an extensive study of this subject. Hydrophobic low boilers to very hydrophobic high boilers have been studied. 

Figure 20-48 shows Wijmans s plot [Wijmans et al.,/. Membr. Sci., 109, 135 (1996)] along with regions where different membrane processes operate (Baker, Membrane Technology and Applications, 2d ed., Wiley, 2004, p. 177). For RO and UF applications, Sj , < 1, and c > Cl,. This may cause precipitation, fouling, or product denatura-tion. For gas separation and pervaporation, Sj , >1 and c < ci. MF is not shown since other transport mechanisms besides Brownian diffusion are at work. 

Pervaporation. Pervaporation differs from the other membrane processes described so far in that the phase-state on one side of the membrane is different from that on the other side. The term pervaporation is a combination of the words permselective and evaporation. The feed to the membrane module is a mixture (e.g. ethanol-water mixture) at a pressure high enough to maintain it in the liquid phase. The liquid mixture is contacted with a dense membrane. The other side of the membrane is maintained at a pressure at or below the dew point of the permeate, thus maintaining it in the vapor phase. The permeate side is often held under vacuum conditions. Pervaporation is potentially useful when separating mixtures that form azeotropes (e.g. ethanol-water mixture). One of the ways to change the vapor-liquid equilibrium to overcome azeotropic behavior is to place a membrane between the vapor and liquid phases. Temperatures are restricted to below 100°C, and as with other liquid membrane processes, feed pretreatment and membrane cleaning are necessary. 

The catalytic esterification of ethanol and acetic acid to ethyl acetate and water has been taken as a representative example to emphasize the potential advantages of the application of membrane technology compared with conventional distillation [48], see Fig. 13.6. From the McCabe-Thiele diagram for the separation of ethanol-water mixtures it follows that pervaporation can reach high water selectivities at the azeotropic point in contrast to the distillation process. Considering the economic evaluation of membrane-assisted esterifications compared with the conventional distillation technique, a decrease of 75% in energy input and 50% lower investment and operation costs can be calculated. The characteristics of the membrane and the module design mainly determine the investment costs of membrane processes, whereas the operational costs are influenced by the hfetime of the membranes. 

Keywords Membranes Selectivity Separations Transport processes Pervaporation Acetic acid-water mixtures Poly(vinyl alcohol) membranes Graft copolymerization... 

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 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. 

Pervaporation is a concentration-driven membrane process for liquid feeds. It is based on selective sorption of feed compounds into the membrane phase, as a result of differences in membrane-solvent compatibility, often referred to as solubility in the membrane matrix. The concentration difference (or, in fact, the difference in chemical potential) is obtained by applying a vacuum at the permeate side, so that transport through the membrane matrix occurs by diffusion in a transition from liquid to vapor conditions (Figure 3.1). Alternatively, a sweep gas can be used to obtain low vapor pressures at the permeate side with the same effect of a chemical potential gradient. 

Solvent-resistant nanofiltration and pervaporation are undoubtedly the membrane processes needed for a totally new approach in the chemical process industry, the pharmaceutical industry and similar industrial activities. This is generally referred to as process intensification and should allow energy savings, safer production, improved cost efficiency, and allow new separations to be carried out. 

Problems to be solved are related to membrane stability (of polymeric membranes, but also the development of hydrophobic ceramic nanofiltration membranes and pervaporation membranes resistant to extreme conditions), to a lack of fundamental knowledge on transport mechanisms and models, and to the need for simulation tools to be able to predict the performance of solvent-resistant nanofiltration and pervaporation in a process environment. This will require an investment in basic and applied research, but will generate a breakthrough in important societal issues such as energy consumption, global warming and the development of a sustainable chemical industry. 

These compounds are commonly present in complex fermentation media, or even in natural raw materials and subsidiary streams resulting from the processing of these materials. Their recovery is usually difficult due to their low concentration, often vestigiary, and the complexity of the original matrix where they have to be recovered from. This chapter discusses, and illustrates with recent applications, the use of different membrane processes able to deal with the recovery of small biologically active molecules (see Figure 11.2) electrodialysis, pervaporation, and nanofiltration. 

Catalytic reactions can be combined in membrane-assisted integrated catalytic processes with practically all the membrane unit operations available today. Many examples of integration of membrane contactors, pervaporation, gas separation, nanofiltration, microfiltration, and ultrafiltration operations together with catalytic reactions, have been proposed in the literature. 

Separation of isopropanol (IPA) and water by pervaporation has also reached production scale. Much of the current capacity is devoted to azeotrope breaking and dehydration during IPA synthesis. Recently, anhydrous isopropanol has become a preferred drying solvent in the semiconductor industry, where chip wafers are first washed with ultrapure water, then rinsed with the alcohol to promote uniform drying. The water-laden isopropanol generated can be conveniently reused after dehydration by pervaporation. Unlike with pressure-driven membrane processes such as RO or UF, particulates and nonvolatile substances such as salts are not carried over during pervaporation. This helps maintain the effectiveness of contamination control. 

One approach to delivering increased performance in a membrane process is to complement one separation mechanism with another. Vapor-arbitrated pervaporation is an example of this strategy. In bioseparations, as will be covered in a later section, a similar integration of several process enhancements in High-Performance Tangential How Filtration is responsible for dramatic improvement in separation efficiency of protein mixtures once considered unachievable by means of conventional ultrafiltration. 

Separation of cthanol/watcr mixtures Pervaporation is a developing membrane process which has elements of reverse osmosis and gas separation. In pervaporation, a liquid mixture is brought in contact with one side of a membrane while the permeate is removed as a vapor from the other side. The driving force is the difference tween the partial pressure of the feed stream and the vapor pressure on the permeate side. 

Very low capital and operating cost The separation could be made more economical by using a hybrid membrane process, i.e., a combination of distillation and pervaporation processes. Thus, a part of the total separation employs distillation where it is economical. PV replaces the subsequent separation where distillation becomes expensive. The overall operating cost of such a hybrid process is much lower than that of distillation alone. 

Selective separation of hquids by pervaporation is a result of selective sorption and diffusion of a component through the membrane. PV process differs from other membrane processes in the fact that there is a phase change of the permeating molecules on the downstream face of the membrane. PV mechanism can be described by the solution-diffusion mechanism proposed by Binning et al. [3]. According to this model, selective sorption of the component of a hquid mixture takes place at the upstream face of the membrane followed by diffusion through the membrane and desorption on the permeate side. 

Desorption on the downstream side of the membrane is generally considered to be rapid and nonselective. The gas phase diffusivities in the final step of transport are very high and hence this step offers the least resistance in the overall transport process. As a separation process, pervaporation relies on the difference in membrane permeabilities, which are dependent on the thermodynamics activities of the components to be separated. 

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