Carbon dioxide solvent power

Supercritical fluids can be highly selective and their solvent power can be controlled by adjustment of the operating pressure. With fluids such as carbon dioxide, there is no residual contamination of the product as the solvent evaporates completely at the end of the operation. 

In packed column SFC, polar solutes such as amines and carboxylic acids often have too much retention or elute with poor peak shapes when neat carbon dioxide is used as a mobile phase [28, 92]. This is mainly due to the weak solvent strength of neat carbon dioxide compared to a liquid solvent. The use of modifiers is often necessary to enhance the solvating power of the mobile phase in SFC. Various alcohols such as methanol and isopropanol are commonly used modifiers in SFC, but other solvents such as acetonitrile was also utilized [92]. The concentrations of modifiers are usually less than 50%. The technique in which the concentrations of modifiers are greater than 50% is often called enhanced-fluidity liquid chromatography [93]. 

Enhanced-fluidity liquids (EELs) are mixtures that contain high proportions of liquefied gases, such as carbon dioxide [5]. Eluidity,/, is defined as the inverse of viscosity. EEL mixtures combine the positive attributes of commonly-used liquids, such as high solvent strength, with the positive attributes of supercritical fluids, such as low viscosity or high fluidity, low surface tension, high diffusivity. These attributes allow EELC to contribute to the quest for increased separation power. 

Carbon dioxide has a conveniently low critical point (31 °C, 7.39 MPa), and supercritical CO2 has become the most widely used fluid where supercritical solvent properties are required, as it is also inexpensive and nontoxic. The solvent powers of supercritical fluids generally increase with increasing density, which can be regulated at will by varying the pressure. The absence of a gas-liquid interface and associated surface tension in a supercritical fluid enables the fluid to penetrate porous solids freely, and also to... 

The solvent power of supercritical carbon dioxide is relatively weak and is strongly linked to its density (controlled by pressure and temperature), but it can be increased by adding a polar organic solvent (referred to as co-solvent) such as methanol or acetonitrile. 

In general, volatile components can be extracted from the dried raw materials under conditions close to the critical point of carbon dioxide. Temperatures should be within the range of 32 to 60°C. However, some heat-sensitive components may decompose, even below this range. Extraction pressures should be between 74 and 120 bar, since at higher pressures the increased solvent power of CO2 also increases the solubility of unwanted components. The yields obtained by SFE are very similar to those found by steam distillation. However, even under mild extraction conditions, some small amount of cuticular waxes is co-extracted with the volatiles. The major constituents of the waxes are -paraffins, ranging from C25 to... 

Existing physical absorption AGR processes are relatively energy inefficient for application in coal gasification they use substantial amounts of steam or stripping gas to regenerate lean solvent and power to pump lean solvent into the AGR absorber. In the treatment of crude gas with substantial carbon dioxide content, work available by expansion of separated carbon dioxide from its partial pressure in the crude gas, typically 100-300 psia, to atmospheric pressure, is not recovered. In theory, an AGR process could recover and utilize this potential energy. 

Carbon dioxide (CO2) has a low supercritical temperature (31°C) and pressure (73 atm). It is nontoxic and nonflammable and is available at high purity. Therefore, CO2 has become the solvent of choice for most SFE applications. Being nonpolar and without permanent dipole moment, supercritical CO2 is a good solvent for the extraction of nonpolar and moderately polar compounds. However, its solvating power for polar solutes is rather poor. Moreover, when the solutes bind strongly to the matrix, the solvent strength of CO2 is often inadequate to break the solute-matrix bond. 

Based on its ability to enhance solvating power by increasing fluid density, supercritical fluid extraction offers an attractive alternative for fractionation of fats and oils. It works by the phenomena of selective distillation and simultaneous extraction, as has been shown by many researchers [3-5]. While the use of supercritical fluids in the extraction of numerous biomaterials has been reported, its commercialization has been limited to the decaffeination of coffee and tea and to the extraction of flavors from hops and spices. The chemical complexity of most food ingredients and their tendency to react and degrade at elevated temperatures, emphasize the difficulties of supercritical solvent selection. Carbon dioxide is the preferred supercritical solvent (its properties have previously been cited [6]). 

The extraction yield rises with pressure at 313 K due to the increasing of the supercritical CO2 density as the pressure increases at constant temperature, increasing the solvent power of carbon dioxide. The yield of extraction with liquid CO2 was lower than with supercritical CO2. No differences in extractions results were observed with the two types of oregano used. 

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