Mass transfer properties supercritical fluids

Table 3.3 presents the approximate physical properties of gases, supercritical fluids, and liquids. It shows that the densities of supercritical fluids are close to that of a liquid, whereas their viscosities are gaslike. The diffusion coefficients are in between. Due to these unique properties, supercritical fluids have good solvating power (like liquid), high diffusivity (better than liquid), low viscosity, and minimal surface tension (like gas). With rapid mass transfer in the supercritical phase and with better ability to penetrate the pores in a matrix, extraction is fast in SFE, along with high extraction efficiency. 

During the extraction phase the whole mass transfer may be regarded as a quasi-stationary process. Scale-up rules therefore take account of external mass transfer from the solid surface to the supercritical fluid only. If pilot and production plants are required to display the same mass transfer properties, then... 

If the polarity is considered equivalent to hexane and polar modifiers are added to the supercritical fluid, then the separation may be considered similar to normal-phase HPLC. However, the viscosity and mass transfer properties of supercritical fluids are more favorable and can lead to increased separation efficiencies and decreased analysis times. Berger and Wilson,for example, have demonstrated that separations with up to 260,000 theoretical plates can be achieved by serially coupling 10 HPLC columns without the deleterious pressure effects that would be encountered in separations using a liquid mobile phase. For applications that are not limited by polar matrices, SFC is, therefore, a viable option. 

Perhaps the most often misinterpreted properties of supercritical fluids are their mass transfer properties. It is often claimed that SCF extraction processes... 

Supercritical Fluid Chromatography and Extraction A separation technique similar to other extraction and chromatographic methods, but in which the mobile phase is actually a fluid in its supercritical fluid state. A supercritical fluid is a fluid that is held above its critical temperature and pressure, and for which no application of additional pressure can result in the development of a liquid phase. Supercritical fluids are unique in that while they possess liquid like densities, the mass transfer properties are very much like those of liquids. Supercritical fluid chromatography remains a niche method that is applicable to pharmaceuticals and other high relative molecular mass solutes. Supercritical extraction, on the other hand, is more widely used as a sample preparation method, especially in pharmaceutical analyses, polymers, and environmental analyses. 

Some investigations were made to compare supercritical fluids with organic solvents like -hexane. In 1988, Chi [75] examined the hydrolysis and esterification of triolein. They found a fourfold increase of the initial reaction rate when using SCCO2 instead of n-hexane. These results were explained with the better mass transfer properties of SCCO2 and the higher dielectric constant of water in the microenvironment of the enzyme. 

A supercritical fluid exhibits physical-chemical properties intermediate between those of liquids and gases. Mass transfer is rapid with supercritical fluids. Their dynamic viscosities are nearer to those in normal gaseous states. In the vicinity of the critical point the diffusion coefficient is more than 10 times that of a liquid. Carbon dioxide can be compressed readily to form a liquid. Under typical borehole conditions, carbon dioxide is a supercritical fluid. 

Supercritical fluids possess favorable physical properties that result in good behavior for mass transfer of solutes in a column. Some important physical properties of liquids, gases, and supercritical fluids are compared in Table 4.1 [49]. It can be seen that solute diffusion coefficients are greater in a supercritical fluid than in a liquid phase. When compared to HPLC, higher analyte diffusivity leads to lower mass transfer resistance, which results in sharper peaks. Higher diffusivity also results in higher optimum linear velocities, since the optimum linear velocity for a packed column is proportional to the diffusion coefficient of the mobile phase for liquid-like fluids [50, 51]. 

Supercritical fluid chromatography (SFC) is an intermediate chromatographic technique between GC and HPLC. It depends upon the fact that when a fluid becomes supercritical (both the temperature and pressure are at or above its critical point) it develops some of the solvating properties of a liquid whilst retaining the low viscosity of a gas. Hence, mass transfer (essential to efficient chromatography) is more akin to that of GC than HPLC, but many compounds can be chromatographed at temperatures much lower than what would be required by GC, so some thermally labile compounds are amenable to SFC where they would degrade under GC conditions [28]. 

The benefits from tuning the solvent system can be tremendous. Again, remarkable opportunities exist for the fruitful exploitation of the special properties of supercritical and near-critical fluids as solvents for chemical reactions. Solution properties may be tuned, with thermodynamic conditions or cosolvents, to modify rates, yields, and selectivities, and supercritical fluids offer greatly enhanced mass transfer for heterogeneous reactions. Also, both supercritical fluids and near-critical water can often replace environmentally undesirable solvents or catalysts, or avoid undesirable byproducts. Furthermore, rational design of solvent systems can also modify reactions to facilitate process separations (Eckert and Chandler, 1998). 

A number of other methods, not falling within any of the earlier-mentioned categories, may prove useful for process intensification. Some of them, such as supercritical fluids, are already known and have been applied in other industries (104,105). Because of their unique properties, especially the high diffusion coefficient, supercritical fluids are attractive media for mass transfer operations,... 

In these systems, the interface between two phases is located at the high-throughput membrane porous matrix level. Physicochemical, structural and geometrical properties of porous meso- and microporous membranes are exploited to facilitate mass transfer between two contacting immiscible phases, e.g., gas-liquid, vapor-liquid, liquid-liquid, liquid-supercritical fluid, etc., without dispersing one phase in the other (except for membrane emulsification, where two phases are contacted and then dispersed drop by drop one into another under precise controlled conditions). Separation depends primarily on phase equilibrium. Membrane-based absorbers and strippers, extractors and back extractors, supported gas membrane-based processes and osmotic distillation are examples of such processes that have already been in some cases commercialized. Membrane distillation, membrane... 

Therefore a much higher mass transfer coefficient can be expected for SFE. A comparison of countercurrent extraction columns using supercritical fluids with those using liquid solvents shows, however, that SFE-columns do not reach an efficiency as high as could be expected because of the solvent properties (table 2). 

A major chemical engineering task in supercritical fluid extraction is the optimisation of temperature and pressure. A thorough knowledge of physical properties, in particular phase equilibria, and of mass transfer as a function of pressure and temperature is required. 

Supercritical fluids possess characteristics that make them interesting for use as polymerization media. A supercritical fluid exists at temperatures and pressures above its critical values. In the supercritical state, the fluid exhibits physical and transport properties intermediate between the gaseous and liquid state. This is illustrated in Table 2. SCFs have liquid-like densities, but gas-like diffusivities. These intermediate properties can provide advantages over liquid-based processes. In particular, the higher diffusivities of SCFs reduce mass transfer limitations in diffusion-controlled processes. Additionally, lower energy is required for processing the supercritical fluid because its viscosity is lower than that of most liquids, and because the need to vaporize large quantities of liquid is avoided. 

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. 

The development of mass transfer models require knowledge of three properties the diffusion coefficient of the solute, the viscosity of the SCF, and the density of the SCF phase. These properties can be used to correlate mass transfer coefficients. At 35 C and pressures lower than the critical pressure (72.83 atm for CO2) we use the diffusivity interpolated from literature diffusivity data (2,3). However, a linear relationship between log Dv and p at constant temperature has been presented by several researchers U>5) who correlated diffusivities in supercritical fluids. For pressures higher than the critical, we determined an analytical relationship using the diffusivity data obtained for the C02 naphthalene system by lomtev and Tsekhanskaya (6), at 35 C. 

---