Organics pervaporation

Table Al.ll Organic Pervaporation Behavior of Organic/Water Systems for Selected Membranes...

Most solution-cast composite membranes are prepared by a technique pioneered at UOP (35). In this technique, a polymer solution is cast directly onto the microporous support film. The support film must be clean, defect-free, and very finely microporous, to prevent penetration of the coating solution into the pores. If these conditions are met, the support can be coated with a Hquid layer 50—100 p.m thick, which after evaporation leaves a thin permselective film, 0.5—2 pm thick. This technique was used to form the Monsanto Prism gas separation membranes (6) and at Membrane Technology and Research to form pervaporation and organic vapor—air separation membranes (36,37) (Fig. 16). 

Pervaporation is a relatively new process with elements in common with reverse osmosis and gas separation. In pervaporation, a liquid mixture contacts one side of a membrane, and the permeate is removed as a vapor from the other. Currendy, the only industrial application of pervaporation is the dehydration of organic solvents, in particular, the dehydration of 90—95% ethanol solutions, a difficult separation problem because an ethanol—water azeotrope forms at 95% ethanol. However, pervaporation processes are also being developed for the removal of dissolved organics from water and the separation of organic solvent mixtures. These applications are likely to become commercial after the year 2000. 

Pervaporation has been commercialized for two appHcations. The first and most developed is the separation of water from concentrated alcohol solutions. GFT of Neunkirchen, Germany, the leader in this field, installed their first important plant in 1982. More than 100 plants have been installed by GFT for this appHcation (90). The second appHcation is the separation of small amounts of organic solvents from contaminated water (91). In both of these apphcations, organics are separated from water. This separation is relatively easy, because organic compounds and water, due to their difference in polarity, exhibit distinct membrane permeation properties. The separation is also amenable to membrane pervaporation because the feed solutions are relatively nonaggressive and do not chemically degrade the membrane. 

In the flow schematic (Fig. 22-80), the condenser controls the vapor pressure of the permeating component. The vacuum pump, as shown, pumps both hqiiid and vapor phases from the condenser. Its major duty is the removal of noncondensibles. Early work in pervaporation focused on organic-organic separations. Many have been demonstrated few if any have oeen commerciaHzed. Still, there are prospects for some difficult organic separations. 

Pervaporation membranes are of two general types. Hydrophilic membranes are used to remove water from organic solutions, often from azeotropes. Hydrophobic membranes are used to remove organic compounds from water. The important operating charac teris-tics of hydrophobic and hydrophihc membranes differ. Hydrophobic membranes are usually used where the solvent concentration is about... 

Dehydration The growing use of isopropanol as a clean-rinse fluid in microelectronics produces significant quantities of an 8.5-90 percent isopropanol waste. Removing the water and trace contan ii-nants is required before the alcohol can be reused. Pervaporation produces a 99.99 percent alcohol product in one step. It is subsequently polished to remove metals and organics. In Europe, dehydration or ethanol is the largest pei vaporation application. For the very large ethanol plants typical of the United States, pei vaporation is not competitive with thermally integrated distillation. 

Pervaporation Liquid Vapor 1.5-60 (permeate is under vacuum) Nonporous Volatile organic compounds... 

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. 

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. 

Volkov (1994) has given a state-of-the-art review on pervaporation. A number of industrial plants exist for dehydration of ethanol-water and (.vwpropanol-water azeotropes, dehydration of ethyl acetate, etc. There is considerable potential in removing dissolved water from benzene by pervaporation. The recovery of dis.solved organics like CH2CI2, CHCI3, CCI4, etc. from aqueous waste streams also lends itself for pervaporation and pilot plants already exist. 

Organic from Water An area where pervaporation may become important is in flavors, fragrances, and essential oils. Here, high-value materials with unique properties are recovered from aqueous or alcohol solutions. 

Pollution Control Pervaporation is used to reduce the organic loading of a waste stream, thus effecting product recovery and a reduction in waste-treatment costs. An illustration is a waste stream containing II percent (wt) n-propanol. The residue is stripped to 0.5 percent and 96 percent of the alcohol is recovered in the permeate as a 45 percent solution. This application uses a hydrophobic, rubbery membrane. The residue is sent to a conventional waste-treatment plant. 

Membranes can also be used to alter the vapor-liquid equilibrium behavior and allow separation of azeotropes. The liquid mixture is fed to one side of the membrane, and the permeate is held under conditions to maintain it in the vapor phase. Most separations use hydrophyllic membranes that preferentially pass water rather than organic material. Thus, pervaporation is commonly used for the dehydration of organic components. 

Grafting of functional monomers onto fluoropolymers produced a wide variety of permselective membranes. Grafting of styrene (with the following sulfonation), (meth)acrylic acids, 4-vinylpyridine, A-vinylpyrrolidone onto PTFE films gave membranes for reverse omosis,32-34 ion-exchange membrane,35-39 membranes for separating water from organic solvents by pervaporation,49-42 as well as other kinds of valuable membranes. 

The pervaporation separation of water-phenol mixtures was carried out using poly(vinyl alcohol) (PVA) cross-linked membranes with low molecular weight poly(aciylic acid) (PAA), at 30, 40, and 50 °C. They have used pervaporation because the separation rate is higher (for liquid organic mixtures) in pervaporation than in reverse osmosis. 

Alcohol is a clean energy source that can be produced by the fermentation of biomass. However, it needs to be highly concentrated. In general, aqueous alcohol solutions are concentrated by distillation, but an azeotrope (96.5 wt% ethanol) prevents further separated by distillation. Pervaporation, a membrane separation technique, can be used for separation of these azeotropes pervaporation is a promising membrane technique for the separation of organic liquid mixtures such as azeotropic mixtures [34] or close-boiling point mixtures. 

Novel hydrophilic polymer membranes based on crosslinked poly(allylamine hydrochloride) (PAA.HCl)-PVA have been developed in order to dehydrate different organic compounds by pervaporation [33], The characteristics of the acetone dehydration process,... 

The blend membranes are permselective for different organic isomers. So, these could be used for the separation of n-propanol from a mixture of n-propanol (n-PrOH) and i-propanol (i-PrOH) [84] and the separation of p-xylene from a p-xylene and o-xylene mixture [35], It was evidenced that, in both cases, the separation was better by applying the evapomeation technique than that of the pervaporation. 

K., Kondo, M., and NaA, Z. (2001) membrane preparation, single-gas permeation, and pervaporation and vapor permeation of water/organic liquid mixtures. Ind. Eng. Chem. Res., 40, 163-175. 

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