Pervaporation modeling

J. Lipzinski, G. Tragardh, 2001, Modelling of Pervaporation, Models to analyze and prediet the mass transfer transport in Pervaporation, Separation and Purifieation Methods, vol. 30(1), 49-25. 

Tyagi, R.K., Fouda, A.E. and Matsuura, T. 1995. A pervaporation model Membrane design. 

Brazinha C and Crespo J G (2009), Aroma recovery from hydro alcoholic solutions by organophihc pervaporation modelling of fractionation by condensation , / Membr Sci, 341,109-121. 

Industrial applications began in the 1970s. This was made possible by the development of highly selective polyvinyl alcohol composite membranes. The process is clearly discussed by Sander and Soukup. They provide engineering performance curves for removing water from an ethanol-water mixture. The curves show how the temperature and ethanol concentration of the feed affect the flux of water through the membrane and the composition of the permeate stream. These performance curves are used in this chapter to provide a simple pervaporation model that captures the behavior of the process with sufficient fidelity for use in control studies. 

This chapter has studied the control of a column-pervaporation process for producing high-purity ethanol to overcome the azeotropic limitation encountered in distillation. A conventional control structure is developed that provides effective dismrbance rejection for both production rate and feed composition changes. A simple pervaporation model is developed in Aspen Custom Modeler that captures the important dynamic features of the process. The model uses pervaporation characteristic performance curves to determine diffusivities. Component fluxes depend upon composition driving forces between the retentate and permeate sides of the membrane. The dynamics of the pervaporation cells are assumed to be dominated by composition and energy capacitance of the liquid retentate. 

H. O. E. Karlsson, G. Tragadh. Pervaporation of dilute organic waters mixtures A literature review on modeling studies and applications to aroma recovery. J Membr Sci 75 121, 1993. 

Dense membranes are used for pervaporation, as for reverse osmosis, and the process can be described by a solution-diffusion model. That is, in an ideal case there is equilibrium at the membrane interfaces and diffusional transport of components through the bulk of the membrane. The activity of a component on the feed side of the membrane is proportional to the composition of that component in the feed solution. 

The composition at the permeate-phase interface depends on the partial pressure and saturation vapour pressure of the component. Solvent composition within the membrane may vary considerably between the feed and permeate sides interface in pervaporation. By lowering the pressure at the permeate side, very low concentrations can be achieved while the solvent concentration on the feed-side can be up to 90 per cent by mass. Thus, in contrast to reverse osmosis, where such differences are not observed in practice, the modelling of material transport in pervaporation must take into account the concentration dependence of the diffusion coefficients. 

A process performance study has been conducted by David et al. [47] taking the coupling of pervaporation with the esterification reactions of 1-propanol and 2-pro-panol with propionic acid as a model system. Toluene sulfonic acid was appHed as the homogeneous acid catalyst A PVA-based composite membrane from GFT was used. Fig. 13.5 shows the comparison between the esterification reaction with and without pervaporation. Without pervaporation, the conversion factor reaches a hm-it, which corresponds to the equihbrium of the esterification reaction. Coupling of the esterification to pervaporation allows the reaction to reach almost complete conversion. 

Based on experimental results and a model describing the kinetics of the system, it has been found that the temperature has the strongest influence on the performance of the system as it affects both the kinetics of esterification and of pervaporation. The rate of reaction increases with temperature according to Arrhenius law, whereas an increased temperature accelerates the pervaporation process also. Consequently, the water content decreases much faster at a higher temperature. The second important parameter is the initial molar ratio of the reactants involved. It has to be noted, however, that a deviation in the initial molar ratio from the stoichiometric value requires a rather expensive separation step to recover the unreacted component afterwards. The third factor is the ratio of membrane area to reaction volume, at least in the case of a batch reactor. For continuous opera-... 

Fig. 19.3 The solution-diffusion transport model in pervaporation. a Solution of compounds from the feed phase into the membrane surface, b Diffusion across the membrane barrier, c Desorption from the membrane permeate (downstream) side into the permeate phase...

Most research on aroma recovery by organophilic pervaporation has been conducted using aqueous aroma model solutions [25-28], although in recent years significant interest has been devoted to the recovery of aroma compounds from natural complex streams, such as fruit juices [29-31], food industry effluents [32] and other natural matrixes [33]. The increasing demand for natural aroma compounds for food use, and their market value, opens a world of possibilities for a technique that allows for a benign recovery of these compounds without addition of any chemicals or temperature increase. However, in most situations, dedicated requests by industrialists are formulated in cooperation with marketing departments, which translate into the need for a correct public perception. 

C.K. Yeom, R.Y.M. Huang, Modelling of the pervaporation separation of ethanol—water mixtures through crosslinked poly(vinyl alcohol) membrane, J. Membr. Sci. 67 (1992) 39—55. 

Reverse osmosis, pervaporation and polymeric gas separation membranes have a dense polymer layer with no visible pores, in which the separation occurs. These membranes show different transport rates for molecules as small as 2-5 A in diameter. The fluxes of permeants through these membranes are also much lower than through the microporous membranes. Transport is best described by the solution-diffusion model. The spaces between the polymer chains in these membranes are less than 5 A in diameter and so are within the normal range of thermal motion of the polymer chains that make up the membrane matrix. Molecules permeate the membrane through free volume elements between the polymer chains that are transient on the timescale of the diffusion processes occurring. 

The solution-diffusion model applies to reverse osmosis, pervaporation and gas permeation in polymer films. At first glance these processes appear to be very... 

In this section the solution-diffusion model is used to describe transport in dialysis, reverse osmosis, gas permeation and pervaporation membranes. The resulting equations, linking the driving forces of pressure and concentration with flow, are then shown to be consistent with experimental observations. 

Figure 2.12 Chemical potential, pressure, and activity profiles through a pervaporation membrane following the solution-diffusion model...

Sorption data were used to obtain values for A" L. As pointed out by Paul and Paciotti, the data in Figure 2.17 show that reverse osmosis and pervaporation obey one unique transport equation—Fick s law. In other words, transport follows the solution-diffusion model. The slope of the curve decreases at the higher concentration differences, that is, at smaller values for c,eimi because of decreases in the diffusion coefficient, as the swelling of the membrane decreases. 

Figure 9.3 The pervaporation process shown in Figure 9.1 can be described by the thermodynamically equivalent process illustrated here. In this model the total pervaporation separation /9pervap is made up of an evaporation step followed by a membrane permeation step [18]...

Concentration polarization can dominate the transmembrane flux in UF, and this can be described by boundary-layer models. Because the fluxes through nonporous barriers are lower than in UF, polarization effects are less important in reverse osmosis (RO), nanofiltration (NF), pervaporation (PV), electrodialysis (ED) or carrier-mediated separation. Interactions between substances in the feed and the membrane surface (adsorption, fouling) may also significantly influence the separation performance fouling is especially strong with aqueous feeds. 

Pervaporation with ceramic membranes is less well understood in terms of transport mechanisms. Consequently, modeling of ceramic pervaporation is still less mature, although the performance of the process was reported to be good [89]. Nomura et al. [90] studied the transport mechanism of ethanol/water through silicalite membranes in... 

Krishna and Paschek [91] employed the Maxwell-Stefan description for mass transport of alkanes through silicalite membranes, but did not consider more complex (e.g., unsaturated or branched) hydrocarbons. Kapteijn et al. [92] and Bakker et al. [93] applied the Maxwell-Stefan model for hydrocarbon permeation through silicalite membranes. Flanders et al. [94] studied separation of C6 isomers by pervaporation through ZSM-5 membranes and found that separation was due to shape selectivity. 

Several authors have already developed methodologies for the simulation of hybrid distillation-pervaporation processes. Short-cut methods were developed by Moganti et al. [95] and Stephan et al. [96]. Due to simplifications such as the use of constant relative volatility, one-phase sidestreams, perfect mixing on feed and permeate sides of the membrane, and simple membrane transport models, the results obtained should only be considered qualitative in nature. Verhoef et al. [97] used a quantitative approach for simulation, based on simplified calculations in Aspen Plus/Excel VBA. Hommerich and Rautenbach [98] describe the design and optimization of combined pervaporation-distillation processes, incorporating a user-written routine for pervaporation into the Aspen Plus simulation software. This is an improvement over most approaches with respect to accuracy, although the membrane model itself is still quite... 

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. 

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. 

Brun et al. [43] described binary pervaporative transport using an exponential diffusion model that is dependent on individual component concentrations ... 

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