Supercritical pressure temperature

Eig. 1. Schematic pressure—temperature diagram for a pure material showing the supercritical fluid region, where is the pure component critical point... 

Designs include the once-through boiler, which can operate at sub-critical, critical, or supercritical pressures and at all commercial temperatures, and the radiant boiler, where heat absorption is largely by radiant energy transfer. 

C02 is supercritical at temperatures and pressures above the critical point. 

Brady et al. [52] have discussed pressure-temperature phase diagrams for carbon dioxide polychlorobiphenyls and examined the rate process of desorption from soils. Supercritical carbon dioxide was used to extract polychlorobiphenyls and DDT and Toxaphene from contaminated soils. 

The supercritical liquid region, limited to supercritical pressures and subcritical temperatures. 

High-pressure FT-IR spectroscopy has been used to clarify (1) the rotational isomerism of molecules, (2) characteristics of water and the water-head group, and (3) RSO3 Na4- interactions in reverse micellar aggregates in supercritical ethane. This work demonstrates interesting pressure, temperature, and salt effects on an enzyme-catalyzed esterification and/or maintenance of a one-phase microemulsion in supercritical fluids from practical and theoretical points of view (Ikushima, 1997). 

Extraction of 25 different binary mixtures of racemic acids (2-(4-isobutylphenyl)-propionic acid (1), and cis- and trans-chrysanthemic (2)), and various chiral bases with supercritical carbon dioxide permitted the conclusion that molecular chiral differentiation in a supercritical fluid is more efficient than in conventional solvents. In the majority of cases, however, complete separation could not be achieved. In five cases, remarkable partial resolutions were realized (30-75% ee) and resolution was possible on a preparative scale. The pair ds-chrysanthemic acid and (S)-(-i-)-2-(benzylamino)-1-butanol (3) was studied in detail. Pressure, temperature, and time, as well as the molar ratio of base and acid, had a marked influence on the quantity and quality of the products. Increasing pressure or decreasing temperature resulted in higher ee values. (-)-cw-Chrysanthemic acid in 99% ee was obtained from the raffinate in a single extraction step. Multiple extractions produced the (-i-)-cA-acid in 90% ee (see fig. 6.3) (Simandi et al., 1997). 

In summary, there are four major parameters in SFE that can be modified to obtain good selectivity pressure, temperature, extraction period and choice of modifier. Supercritical fluid extraction is easily automated and can be economically viable if the number of samples is large. 

The advantage of this extraction method is that the parameters pressure, temperature and solvent to feed ratio can be varied in each extraction step. By this way a very accurate fractionation of the different compounds included in the feed can be achieved. The solubility of the compounds in the supercritical fluid, depending on pressure and temperature, can be changed in each extraction step. The highly soluble substances are extracted in the first step at low fluid density. Increasing the density in the following extraction steps leads to the removal of the less soluble substances. Further, the flow rate of the supercritical fluid can be adjusted in each extraction step, either constant flow for each step or different flow rates, depending on the separation to be achieved. 

Gas anti-solvent experiments for different products using supercritical carbon dioxide (CO2) Process Substance Solvent Pressure Temperature Particle Ref. 

Supercritical fluid extraction conditions were investigated in terms of mobile phase modifier, pressure, temperature and flow rate to improve extraction efficiency (104). High extraction efficiencies, up to 100%, in short times were reported. Relationships between extraction efficiency in supercritical fluid extraction and chromatographic retention in SFC were proposed. The effects of pressure and temperature as well as the advantages of static versus dynamic extraction were explored for PCB extraction in environmental analysis (105). High resolution GC was coupled with SFE in these experiments. 

Samples of sand spiked with 36 nitroaromatic compounds, 19 haloethers, and 42 organochlorine pesticides, and a standard reference soil (certified for 13 polynuclear aromatic hydrocarbons, dibenzofuran, and pentachlorophenol) were extracted with supercritical carbon dioxide in a two- or four-vessel supercritical fluid extractor to establish the efficiency of the extraction and the degree of agreement of the parallel extraction recoveries. Furthermore, the many variables that influence the extraction process (e.g., flowrate, pressure, temperature, moisture content, cell volume, sample size, extraction time, modifier type, modifier volume, static versus dynamic extraction, volume of solvent in the collection vessel, and the use of glass beads to fill the void volume) were investigated. 

We have demonstrated in this paper that two and four samples can be extracted in parallel with supercritical carbon dioxide without significant impact on data quality. Modifications made to an off-line extractor involved addition of a multiport manifold for the distribution of supercritical fluid to four extraction vessels and of a 12-port, two-way switching valve that allowed collection of two fractions per sample in unattended operation. The only limitation that we have experienced with the four-vessel extraction system was in the duration of the extraction. When working with 2-mL extraction vessels and 50-/zm restrictors, and using the pressure/temperature conditions mentioned above, the 250-mL syringe pump allows us a maximum extraction time of 60 min. During this time, two 30-min fractions can be collected with the present arrangement. 

Figure 15.5. Pressure-temperature phase diagram of pure C02 with a superimposed flow diagram for a closed-loop supercritical fluid treatment process.

The NMR method we have developed gives a direct, in situ determination of the solubility and also allows us to obtain phase data on the system. In this study we have measured the solubilities of solid naphthalene in supercritical carbon dioxide along three isotherms (50.0, 55.0, and 58.5°C) near the UCEP temperature over a pressure range of 120-500 bar. We have also determined the pressure-temperature trace of the S-L-G phase line that terminates with the UCEP for the binary mixture. Finally, we have performed an analysis of our data using a quantitative theory of solubility in supercritical fluids to help establish the location of the UCEP. 

A separation process is sought that can satisfy both our present economic and enviromental constraints. It would also provide an alternative to present practice that relies on expensive azeotropic or extractive distillation processes used in the recovery of products from low relative volatility streams. As an example, virtually all industrial butadiene recovery processes now rely on extractive distillation using acetonitrile or other equivalent agent to enhance the relative volatility of the C4 components. The use of supercritical or near critical separation of these streams may satisfy these requirements provided certain pressure, temperature and recompression criteria can be met. Such a process would also reduce the need for a complex train of distillation towers. 

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