Supercritical separation process

Solubilitiesattemperaturesand pressures above the critical values of the solvent liave important applications for supercritical separation processes. Examples are extraction of caffeine from coffee beans and separation of asplraltenes from heavy petroleum fractions. For a typical solid/vapor equilibrium (SVE) problem, tire solid/vapor saturation pressure P is very small, and the saturated vapor is for practical purposes an ideal gas. Hence 0 for pure solute vapor at this pressure is close to unity. Moreover, exceptfor very low values of the system pressure P, the solid solubility yj is small, and can be approximated by j, the vapor-phase fugacity coefficient of the solute at infinite dilution. Finally, since is very small, the pressure difference P — in the Poyntingfactor is nearly equal to P at any pressure where tins factor... 

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. 

The criteria which would be most desirable for industrial application of a separation process involving a supercritical gas may be established by comparing Figs. 3IB, 3ID, and 32. The largest cost in such a process is likely to be that of gas compression. Therefore, the maximum separation possible of the two solvents should occur for the addition of a given amount of gas, and the total pressure required to dissolve this gas should be small. This is the case if the tie lines slope toward the 1-3 binary line and if the gas is readily soluble. In terms of the Margules parameters and Henry s constant, these favorable criteria are ... 

Chromatography is a physical method of separation in which the components to be separated are distributed between two phases, one of which is stationary (the stationary phase), while the other (the mobile phase) moves in a definite direction. A mobile phase is described as a fluid which percolates through or along the stationary bed in a definite direction . It may be a liquid, a gas or a supercritical fluid, while the stationary phase may be a solid, a gel or a liquid. If a liquid, it may be distributed on a solid, which may or may not contribute to the separation process. ... 

The current state of analytical SPE was critically reviewed and no major changes of the technique have been observed. Overviews of the developments of the extraction technologies of secondary metabolites from plant materials refer to three types of conventional extraction techniques that involve the use of solvents, steam, or supercritical fluids. Each technique is described in detail with respect to typical processing parameters and recent developments. Eollowing the discussion of some technical and economic aspects of conventional and novel separation processes, a few general conclusions about the applicabilities of the different types of extraction techniques are drawn. ... 

The two SCFs most often studied—CO2 and water—are the two least expensive of all solvents. CO2 is nontoxic and nonflammable and has a near-ambient critical temperature of 31. UC. CO2 is an environmentally friendly substitute for organic solvents including chlorocarbons and chlorofluorocarbons. Supercritical water (Tc = 374°C) is of interest as a substitute for organic solvents to minimize waste in extraction and reaction processes. Additionally, it is used for hydrothermal oxidation of hazardous organic wastes (also called supercritical water oxidation) and hydrothermal synthesis. (See also Sec. 15 for additional discussion of supercritical fluid separation processes.)... 

Separation-nozzle method, 25 417 Separation of Isotopes by Laser Excitation (SILEX) technology, 25 416-417 Separation processes enhanced, 27 670-673 foams in, 72 19, 21-22 for supercritical fluids, 24 13-14 sustainable development and, 24 175-176... 

Supercritical fluids also find application in the areas of pollution prevention and remediation, and supercritical carbon dioxide is used as a replacement solvent for many hazardous solvents in both extraction and separation processes and also as a reaction medium and in materials processing. Although carbon dioxide is considered as a greenhouse gas , there is actually no net increase in the amount of the gas if it is removed from the environment, used as the solvent instead of a hazardous substance, and returned to the environment. In this way, most of the uses of supercritical carbon dioxide may be considered as environmentally friendly. Because the solubilities of oils and greases in carbon dioxide are high, it is particularly suited to the cleaning of machinery 47 and, as discussed in the literature 48, it is used as a solvent in textile dyeing operations where it is used to treat any dye-laden... 

Although the general principles of separation processes are applicable widely across the process industries, more specialised techniques are now being developed. Reference is made in Chapter 13 to the use of supercritical fluids, such as carbon dioxide, for the extraction of components from naturally produced materials in the food industry, and to the applications of aqueous two-phase systems of low interfacial tensions for the separation of the products from bioreactors, many of which will be degraded by the action of harsh organic solvents. In many cases, biochemical separations may involve separation processes of up to ten stages, possibly with each utilising a different technique. Very often, differences in both physical and chemical properties are utilised. Frequently... 

Supercritical extraction has been used increasingly in recent years for specialized processes. These processes include separation of drugs from plants, oils from vegetable seeds, impurities from labile materials, and chemical feedstocks from coal and petroleum residual. The utility of supercritical extraction processes stems principally from the enhanced solubility characteristics of CO2 near its critical point and the ease with which the solvent can be recovered for recycle. 

Identification of certain key areas in which supercritical fluid processing could be technically, as well as economically, superior to traditional separation processes. 

Supercritical fluid separation processes operate at pressures ranging from 1000 to 4000 lb/in.2, pressures that might be considered high, especially in the foods and essential oils industries. However, because of the factors just listed, supercritical fluid extraction has become eco-... 

High-pressure pilot plants are used for scaling-up the plants for production of chemicals and for separation processes. As an example, a small scale plant for supercritical extraction is shown in Fig. 4.3-33. The pilot plant manufactured by the SITEC-company [50] contains all the components of a large-scale plant to gain, for example, concentrate of hops from the natural product, and is fully equipped with contrail- and measuring devices. On the left -hand side, the extractor can be seen, to which the separator is joined (right hand side). The pilot plant is designed for pressures up to 300 bar and temperatures of 250°C. It is movable, and can be applied to separate different products from sundry natural and other materials. 

G. Brunner, Gas extraction, An introduction to fundamentals of supercritical fluids and the application to separation processes, Steinkopff, Darmstadt, (1994). 

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