Supercritical fluid extraction critical temperature

Supercritical Fluid Extraction. Supercritical fluid (SCF) extraction is a process in which elevated pressure and temperature conditions are used to make a substance exceed a critical point. Once above this critical point, the gas (CO2 is commonly used) exhibits unique solvating properties. The advantages of SCF extraction in foods are that there is no solvent residue in the extracted products, the process can be performed at low temperature, oxygen is excluded, and there is minimal protein degradation (49). One area in which SCF extraction of Hpids from meats maybe appHed is in the production of low fat dried meat ingredients for further processed items. Its apphcation in fresh meat is less successful because the fresh meat contains relatively high levels of moisture (50). 

Supercritical fluid extraction (SFE) is a technique in which a supercritical fluid [formed when the critical temperature Tf) and critical pressure Pf) for the fluid are exceeded simultaneously] is used as an extraction solvent instead of an organic solvent. By far the most common choice of a supercritical fluid is carbon dioxide (CO2) because CO2 has a low critical temperature (re = 31.1 °C), is inexpensive, and is safe." SFE has the advantage of lower viscosity and improved diffusion coefficients relative to traditional organic solvents. Also, if supercritical CO2 is used as the extraction solvent, the solvent (CO2) can easily be removed by bringing the extract to atmospheric pressure. Supercritical CO2 itself is a very nonpolar solvent that may not have broad applicability as an extraction solvent. To overcome this problem, modifiers such as methanol can be used to increase the polarity of the SFE extraction solvent. Another problem associated with SFE using CO2 is the co-extraction of lipids and other nonpolar interferents. To overcome this problem, a combination of SFE with SPE can be used. Stolker et al." provided a review of several SFE/SPE methods described in the literature. 

The first use of supercritical fluid extraction (SFE) as an extraction technique was reported by Zosel [379]. Since then there have been many reports on the use of SFE to extract PCBs, phenols, PAHs, and other organic compounds from particulate matter, soils and sediments [362, 363, 380-389]. The attraction of SFE as an extraction technique is directly related to the unique properties of the supercritical fluid [390]. Supercritical fluids, which have been used, have low viscosities, high diffusion coefficients, and low flammabilities, which are all clearly superior to the organic solvents normally used. Carbon dioxide (C02, [362,363]) is the most common supercritical fluid used for SFE, since it is inexpensive and has a low critical temperature (31.3 °C) and pressure (72.2 bar). Other less commonly used fluids include nitrous oxide (N20), ammonia, fluoro-form, methane, pentane, methanol, ethanol, sulfur hexafluoride (SF6), and dichlorofluoromethane [362, 363, 391]. Most of these fluids are clearly less attractive as solvents in terms of toxicity or as environmentally benign chemicals. Commercial SFE systems are available, but some workers have also made inexpensive modular systems [390]. 

The supercritical fluid extraction (SFE) is a process in which a highly compressed gas (fluid) is brought into contact with a relatively non-volatile solid or liquid at temperatures at or slightly above the critical temperature of the solvent. Under such conditions, the condensed phase will begin to volatize, which is interpreted as the supercritical fluid phase (Vayisoglu et al., 1996). The SFE is one of the best methods to obtain hqnid fuels from coals. The SFE extraction is carried out in an autoclave at above the critical temperature and the pressure of the solvent. The yield of soluble material increases with increasing pressure (Paul and Wise, 1971). 

The properties and physical chemistry of liquid and supercritical carbon dioxide have been extensively reviewed (Kiran and Brennecke, 1992), as have many fundamentals and applications for separation, chromatography, and extraction (McHugh and Krukonis, 1994). The phase diagram for pure C02 is illustrated in Figure 1.1. Due to its relatively low critical point, C02 is frequently used in the supercritical state. Other common supercritical fluids require higher temperatures and pressures, such as water with Tc = 374.2 °C and Pc = 220.5 bar, while propane (Tc = 96.7 °C and Pc = 42.5 bar) and ethane (Tc = 32.2 °C and Pc = 48.8 bar) have lower critical pressures but are flammable (McHugh and Krukonis, 1994). 

Supercritical Fluid Extraction. Conditions can be generated that allow materials to behave differently from their native state. For example, boiling points are defined as that temperature at which a liquid changes to a gas. If the liquid is contained and pressure exerted, the boiling point changes. For a particular liquid, a combination of pressure and temperature will be reached, called the critical point, at which the material is neither a liquid nor a gas. Above this point exists a region, called the supercritical region, at which increases in both pressure and temperature will have no effect on the material (i.e., it will neither condense nor boil). This so-called supercritical fluid will exhibit properties of both a liquid and a gas. The supercritical fluid penetrates materials as if it were a gas and has solvent properties like a liquid. 

Supercritical fluid extraction is an attractive process primarily because the density and solvent power of a fluid changes dramatically with pressure at temperatures near the critical. In complex... 

Table 2 shows critical parameters of the fluids most used for SFE. When it comes to choosing a supercritical fluid, the critical pressure and the critical temperature are two important parameters. The critical pressure determines, from a first approximation, the importance of the solvent power of the fluid. Ethane, for example, which has a lower critical pressure than carbon dioxide, will not dissolve a moderately polar soluble in the same way as carbon dioxide. Similarly, fluids with a higher critical pressure are more able to dissolve polar compounds. The critical temperature has practical implications. Indeed, one should always consider the influence of the extraction temperature on the stability of the component to extract. 

Supercritical fluid extraction (SFE) with carbon dioxide (CO2) has been used as an alternative to the previously mentioned liquid-liquid extraction methods for food samples. One of the main advantages of SFE is that it yields extracts that are free from chemical residues (Spanos et ah, 1993). Where other extraction methods require large amounts of organic solvents that can be costly to purchase and dispose of, SFE is low cost, nontoxic, and environmentally friendly (Marsili and Callahan, 1993). Carbon dioxide is the most commonly used supercritical fluid, as its low critical temperature (31 °C) makes it favorable for the extraction of heat-sensitive carotenoids (Vagi et ah, 2002). 

In addition to common organic solvents, supercritical fluids (scf s) can be used for a great variety of extraction processes [158 165], Supercritical fluid extraction (SFE), mostly carried out with SC-CO2 as eluant, has many advantages compared to extractions with conventional solvents. The solvent strength of a supercritical fluid can easily be controlled by the pressure and temperature used for the extraction at a constant temperature, extraction at lower pressures will favour less polar analytes, while extraction at higher pressures will favour more polar and higher molar mass analytes. As supercritical fluids such as CO2 and N2O have low critical temperatures (tc = 31 °C and 36 °C, respectively), SFE can be performed at moderate temperatures to extract thermolabile compounds. Typical industrial applications using SC-CO2 include caffeine extraction from coffee beans [158] as well as fat and oil extraction from plant and animal tissues [165]. For some physical properties of supercritical solvents, see Section 3.2. 

Supercritical fluid extraction (SFE) utilizes the properties of supercritical fluids for extraction of analytes from solid samples. A supercritical fluid (SCF) is a substance above its critical temperature and pressure, when it is between the typical gas and liquid state. Low viscosity and near-zero surface tension and heat of vaporization allow SCFs to penetrate into solids more rapidly than liquid solvents, which leads to more favorable mass transfer. The density of an SCF is close to the liquid density. 

Supercritical fluids, most commonly carbon(IV) oxide, occasionally modified by a small addition of a polar solvent (methanol, acetonitrile, or water). Supercritical fluid extraction (SEE) uses water as the most popular additive, because increasing the temperature from 50 to 400 °C at a pressure exceeding the critical level makes it possible to achieve transition of extractant from the subcritical to the supercritical state and leaching of the compoimds in the order of polar to moderately polar [86]. 

Supercritical fluid extraction (SFE) is a method that circumvents some problems associated with conventional separation techniques. Carbon dioxide, as an inert, inexpensive, nonflammable, and environmentally acceptable gas is the solvent of choice because of its moderate critical temperature and pressure (76). SFE has been used effectively to refine marine oils and remove cholesterol, polychlorinated biphenyls (PCB), Vitamin E, and other components (77). The disadvantages of this process include the use of extremely high pressures and the high capital cost. 

Supercritical fluid extraction Supercritical fluid extraction (SFE) uses compressed gas as the extraction medium and circumvents some of the problems associated with the use of classical separation techniques involving organic solvents. This technique combines features of distillation (i.e., separation because of differences in component volatiles) and liquid extraction (i.e., separation of components that exhibit little difference in their relative volatilities or that are thermally labile). A number of gases, when compressed isothermally at a temperature greater than their critical temperature and to pressures greater than their critical pressure, exhibit an enhanced solvating power (136), which has been known since the nineteenth century (137, 138), but its actual applications did not come to practice until the late twentieth century. 

Supercritical fluid extraction - also referred to as dense gas extraction or near critical solvent extraction - means that the operational temperature of the process is in the vicinity of the critical temperature of the solvent. Since the extraction of herbal raw materials requires non-drastic gentle process temperatures the choice of suitable near critical solvents is limited to pure or partly halogenated C,-Cj hydrocarbons, dinitrogen monoxide and carbon dioxide. All these solvents, especially carbon dioxide, exhibit favourable properties in view of the afore-mentioned aspects. 

A fluid is supercritical when it is compressed beyond its critical pressure (Pc) and heated beyond its critical temperature (r, ). Supercritical fluid technology has emerged as an important technique for supercritical fluid extraction (SFE). In many of the industrial applications, it has replaced conventional solvent-based or steam extraction processes, mainly due to the quality and the purity of the final product and environmental benefits. 

Supercritical fluid extraction (SFE) A method of extracting analytes from matrices using a supercritical fluid at elevated pressures and temperatures. The term supercritical fluid is used to describe any substance above its critical temperature and critical pressure. 

Supercritical fluid extraction An extraction method where the extraction fluid, usually C02 is present at a pressure and temperature above its critical point. 

This patent is concerned primarily with the polymerization of ethylene at conditions high above its critical temperature and pressure. The Krase and Lawrence patent covers polymerization but it also describes the separation of various oligomers by stagewise pressure reduction. The multistep sequence results in a lower energy recycle/separation process which produces discreet fractions of polyethylene of different molecular weight. A portion of the example and process operation is excerpted from the patent to point out once more that supercritical fluid extraction and separation have been known and understood for 40 to 50 years. 

Supercritical CO2 has been considered as a potential alternative to conventional solvents due to its relative non-toxicity and non-flammability, as well as its low critical temperature and pressure. Supercritical fluid extraction (SFE) has been used for example in the extraction of fatty acids from diverse matrices such as grape seeds , ginseng seeds, wood pulp , and infant formula . The absence of oxygen and light during the supercritical extraction process helps prevent degradation of the extract. For example, Tipsrisukond, et al." found... 

A solute that is a liquid at the temperature of a supercritical extraction has critical properties much closer to the supercritical fluid s critical properties than the solids discussed above. Since the mixture is somewhat less molecularly as3nranetric, the critical temperature of the supercritical fluid lies above the melting temperature of the solute. As a result, the vaporization (L2V) curve is generally the only pure solute property to be of concern on mixture P-T traces. Many literature references are available for mixtures that fall into this category, because these systems comprise the bulk of high pressure vapor-liquid equilibria research of the last century, however, most data are for hydrocarbon related systems and the current interest extends beyond these systems. A few cases of special interest will be mentioned and further information may be found in other references (4-10). 

---