Pervaporation method

Also, membranes from blends of PVA/Poly(aerylie acid) [PAcr.Ac.] show a selective permeability against different components of a liquid mixture. This property of membranes makes them useful for the separation of components from liquid mixtures by the pervaporation method, i.e., for methanol dehydration. 

In oil processing, separation of aromatic isomers Cg (ethylbenzene 7b= 136°C,p-xylene 7b= 138.3°C, m-xylene Ty, = 139.1°C, >-xylene T], = 144.4°C) is required. According to the literary data, the following isomers of hydrocarbons are separated p-xylene/m-xylene, p-xylene/o-xylene, -hexane/2,2-dimethylbutane, -hexane/3-methylpentane, and n-butane/f-butane [8,83,130-137]. Pervaporation method is the most effective for this purpose. To separate the isomers, membranes based on various polymers were used. Good separation for aU isomer mixtures was attained by the polyimide Kapton film (fip = 1.43-2.18) but parylene films and cellulose acetate also exhibited a relatively high separation factor (fip = 1.22-1.56 and /3p = 1.23-1.56, respectively). Temperatures >200°C were required to obtain a reasonable flux through the polyimide film and a pressure of about 20 atm was necessary to keep the feed stream liquid [8]. 

PI materials have been used for the dehydration of water/alcohol mixtures by the pervaporation method.P84 co-PI hollow fibers and zeolite filled P84 CO-PI membranes " have been used for the pervaporation dehydration of isopropanol. In addition, P84 co-PI based dual-layer hollow fiber membranes serve for the dehydration of tetrafluoropropanol. ... 

Solok EK, Sanli O. 2008. Separation characteristics of dimethylformamide/water mixtures using sodium alginate-g-V-vinyl-2-pyrrolidone membranes by pervaporation method. Chem. Eng. Process. 47 633-641. 

Other method used to determine alcohol permeability is the pervaporation method, where the membrane is embedded in a cell and one is continuously fed, by a pump, with a alcohol solution, and the other side is purged with a continuous flow of an inert gas with a fixed flow rate for carrying the permeate to a gas chromatograph [33, 34]. fii this case the state of solvation of the membrane on the gas side is not well defined. 

For water permeation, the measurements were carried out by using a pervaporation method. This differential permeation method allow to obtain the diffusion and permeability coefficients by taking into account the exposed area of the film and the vapor pressure difference across the two sides of the film. 

Problems may arise from the poor water solubUity of the starting substrate, or from the inhibition of cell growth due to either the substrate or the product over a certain threshold concentration. Methods for the continuous addition of substrate at non-harmful concentrations and removal of the product(s) have been developed. Among these, the most effective ones are the pervaporation method [30], or the addition to the culture media of a nonsoluble solid or nonmiscible hydrophobic liquid phase to create a two-phase system in which the desired volatile is sequestered by the solid or the hydrophobic hquid phase. 

Gel support was accomplished by absorbing a polymerization initiator in the micropores and the tube was immersed into the mixed solution of the primary monomer and crosslinking agent. The separation experiment is performed by the pervaporation method. 

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... 

Of these five methods all but pressure-swing distillation can also be used to separate low volatiUty mixtures and all but reactive distillation are discussed herein. It is also possible to combine distillation and other separation techniques such as Hquid—Hquid extraction (see Extraction, liquid-liquid), adsorption (qv), melt crystallization (qv), or pervaporation to complete the separation of azeotropic mixtures. 

Advantages to Membrane Separation This subsertion covers the commercially important membrane applications. AU except electrodialysis are pressure driven. All except pervaporation involve no phase change. All tend to be inherently low-energy consumers in the-oiy if not in practice. They operate by a different mechanism than do other separation methods, so they have a unique profile of strengths and weaknesses. In some cases they provide unusual sharpness of separation, but in most cases they perform a separation at lower cost, provide more valuable products, and do so with fewer undesirable side effects than older separations methods. The membrane interposes a new phase between feed and product. It controls the transfer of mass between feed and product. It is a kinetic, not an equihbrium process. In a separation, a membrane will be selective because it passes some components much more rapidly than others. Many membranes are veiy selective. Membrane separations are often simpler than the alternatives. 

Membrane Pervaporation Since 1987, membrane pei vapora-tion has become widely accepted in the CPI as an effective means of separation and recovery of liquid-phase process streams. It is most commonly used to dehydrate hquid hydrocarbons to yield a high-purity ethanol, isopropanol, and ethylene glycol product. The method basically consists of a selec tively-permeable membrane layer separating a liquid feed stream and a gas phase permeate stream as shown in Fig. 25-19. The permeation rate and selectivity is governed bv the physicochemical composition of the membrane. Pei vaporation differs From reverse osmosis systems in that the permeate rate is not a function of osmotic pressure, since the permeate is maintained at saturation pressure (Ref. 24). 

So far, the separation of azeotropic systems has been restricted to the use of pressure shift and the use of entrainers. The third method is to use a membrane to alter the vapor-liquid equilibrium behavior. Pervaporation differs from other membrane processes in that the phase-state on one side of the membrane is different from the other side. The feed to the membrane is a liquid mixture at a high-enough pressure to maintain it in the liquid phase. The other side of the membrane is maintained at a pressure at or below the dew point of the permeate, maintaining it in the vapor phase. Dense membranes are used for pervaporation, and selectivity results from chemical affinity (see Chapter 10). Most pervaporation membranes in commercial use are hydrophyllic19. This means that they preferentially allow... 

In a previous section, the effect of plasma on PVA surface for pervaporation processes was also mentioned. In fact, plasma treatment is a surface-modification method to control the hydrophilicity-hydrophobicity balance of polymer materials in order to optimize their properties in various domains, such as adhesion, biocompatibility and membrane-separation techniques. Non-porous PVA membranes were prepared by the cast-evaporating method and covered with an allyl alcohol or acrylic acid plasma-polymerized layer the effect of plasma treatment on the increase of PVA membrane surface hydrophobicity was checked [37].The allyl alcohol plasma layer was weakly crosslinked, in contrast to the acrylic acid layer. The best results for the dehydration of ethanol were obtained using allyl alcohol treatment. The selectivity of treated membrane (H20 wt% in the pervaporate in the range 83-92 and a water selectivity, aH2o, of 250 at 25 °C) is higher than that of the non-treated one (aH2o = 19) as well as that of the acrylic acid treated membrane (aH2o = 22). 

Many other methods for separating isotopes have been described. A partial list includes membrane and membrane pervaporation, thermal diffusion of liquids, mass diffusion, electrolysis and electro-migration, differential precipitation, solvent extraction, biological microbial enrichment, and more. Although not discussed in... 

One of the most common liquid-liquid separation methods investigated is pervaporation. This technique is a low-energy alternative for the separation of mixtures that are difficult and expensive to separate by traditional means such as azeotropes and isomers [35]. In pervaporation a liquid feed is vaporized as ittravels... 

Figure 4.9 Derivation of the mass transfer coefficient by Wilson s method. Toluene/water enrichments are plotted as a function of feed solution superficial velocity in pervaporation experiments. Enrichments were measured at different feed solution superficial velocities with spiral-wound membrane modules [15]...

A second method of determining the coefficient ( >,/5) and the intrinsic enrichment of the membrane Ea is to use Equation (4.11). The term ln(l — 1/E) is plotted against the permeate flux measured at constant feed solution flow rates but different permeate pressures or feed solution temperatures. This type of plot is shown in Figure 4.10 for data obtained with aqueous trichloroethane solutions in pervaporation experiments with silicone rubber membranes. 

Figure 9.21 Methods of integrating pervaporation membranes in the recovery of methanol from the MTBE production process [15]. Courtesy of Air Products and Chemicals, Inc., Allentown, PA...

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... 

Although reverse osmosis can be used to separate organic and aqueous-organic liquid mixtures, very high pressures are required. Alternatively, pervaporation can be used in which the species being absorbed by, and transported through, the non-porous membrane are evaporated. This method, which uses much lower pressures than reverse osmosis, but where the heat of vapourisation must be supplied, is used to separate azeotropic mixtures. 

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