Alternative supercritical fluids

The objective of any separation process is to obtain high purity product. Monocrotaline selectivities as high as 40 wt.% were obtained in the above studies. Clearly, significant post-processing would be required to obtain pure monocrotaline from the extract. Two alternative supercritical fluid-based processes were therefore considered in order to obtain pure monocrotaline. 

After adsorption of the biocides, these have to be desorbed and made accessible to analysis. For desorption from PUF the Soxhlet extraction is commonly used. As alternatives supercritical fluid extraction (SFE) with COj and elution with different solvents were tested. 

Alternative supercritical fluids are to be explored in cases where the intrinsic acidity of scC02/aqueous systems is undesirable. 

Due to the low critical temperature and pressure (Tc = 31°C, jPc = 24 bar), SCCO2 is certainly the most investigated supercritical medium, as also witnessed by the examples reported here. However, alternative supercritical fluids must be explored in cases where the intrinsic reactivity of CO2 cannot be neglected. As recently reported, the PT-catalyzed alkylation of phenyl-acetonitrile with ethyl bromide can be conveniently carried out in supercritical ethane in the presence of tetrabutylammonium bromide (TBAB) and solid potassium carbonate as a base (Fig. 13). Under classical liquid-liquid PTC conditions, this reaction typically requires the use of strong aqueous bases (sodium amide,... 

Palenzuela, B. et al.. Bioguided extraction of polyphenols from grape marc by using an alternative supercritical-fluid extraction method based on a liquid solvent trap. Anal. Bioanal. Chem., 378, 2021, 2004. 

Supercritical fluid extraction (SFE) and Solid Phase Extraction (SPE) are excellent alternatives to traditional extraction methods, with both being used independently for clean-up and/or analyte concentration prior to chromatographic analysis. While SFE has been demonstrated to be an excellent method for extracting organic compounds from solid matrices such as soil and food (36, 37), SPE has been mainly used for diluted liquid samples such as water, biological fluids and samples obtained after-liquid-liquid extraction on solid matrices (38, 39). The coupling of these two techniques (SPE-SFE) turns out to be an interesting method for the quantitative transfer... 

There are basically three methods of liquid sampling in GC direct sampling, solid-phase extraction and liquid extraction. The traditional method of treating liquid samples prior to GC injection is liquid-liquid extraction (LLE), but several alternative methods, which reduce or eliminate the use of solvents, are preferred nowadays, such as static and dynamic headspace (DHS) for volatile compounds and supercritical fluid extraction (SFE) and solid-phase extraction (SPE) for semivolatiles. The method chosen depends on concentration and nature of the substances of interest that are present in the liquid. Direct sampling is used when the substances to be assayed are major components of the liquid. The other two extraction procedures are used when the pertinent solutes are present in very low concentration. Modem automated on-line SPE-GC-MS is configured either for at-column conditions or rapid large-volume injection (RLVI). 

Smith and Udseth [154] first described SFE-MS in 1983. Direct fluid injection (DFT) mass spectrometry (DFT-MS, DFI-MS/MS) utilises supercritical fluids for solvation and transfer of materials to a mass-spectrometer chemical ionisation (Cl) source. Extraction with scC02 is compatible with a variety of Cl reagents, which allow a sensitive and selective means for ionising the solute classes of interest. If the interfering effects of the sample matrix cannot be overcome by selective ionisation, techniques based on tandem mass spectrometry can be used [7]. In these cases, a cheaper and more attractive alternative is often to perform some form of chromatography between extraction and detection. In SFE-MS, on-line fractionation using pressure can be used to control SCF solubility to a limited extent. The main features of on-line SFE-MS are summarised in Table 7.20. It appears that the direct introduction into a mass spectrometer of analytes dissolved in supercritical fluids without on-line chromatography has not actively been pursued. 

These alternative processes can be divided into two main categories, those that involve insoluble (Chapter 3) or soluble (Chapter 4) supports coupled with continuous flow operation or filtration on the macro - nano scale, and those in which the catalyst is immobilised in a separate phase from the product. These chapters are introduced by a discussion of aqueous biphasic systems (Chapter 5), which have already been commercialised. Other chapters then discuss newer approaches involving fluorous solvents (Chapter 6), ionic liquids (Chapter 7) and supercritical fluids (Chapter 8). 

For the elucidation of chemical reaction mechanisms, in-situ NMR spectroscopy is an established technique. For investigations at high pressure either sample tubes from sapphire [3] or metallic reactors [4] permitting high pressures and elevated temperatures are used. The latter represent autoclaves, typically machined from copper-beryllium or titanium-aluminum alloys. An earlier version thereof employs separate torus-shaped coils that are imbedded into these reactors permitting in-situ probing of the reactions within their interior. However, in this case certain drawbacks of this concept limit the filling factor of such NMR probes consequently, their sensitivity is relatively low, and so is their resolution. As a superior alternative, the metallic reactor itself may function as the resonator of the NMR probe, in which case no additional coils are required. In this way gas/liquid reactions or reactions within supercritical fluids can be studied... 

Supercritical fluids (e.g. supercritical carbon dioxide, scCCb) are regarded as benign alternatives to organic solvents and there are many examples of their use in chemical synthesis, but usually under homogeneous conditions without the need for other solvents. However, SCCO2 has been combined with ionic liquids for the hydroformylation of 1-octene [16]. Since ionic liquids have no vapour pressure and are essentially insoluble in SCCO2, the product can be extracted from the reaction using CO2 virtually uncontaminated by the rhodium catalyst. This process is not a true biphasic process, as the reaction is carried out in the ionic liquid and the supercritical phase is only added once reaction is complete. 

Supercritical fluids represent a different type of alternative solvent to the others discussed in this book since they are not in the liquid state. A SCF is defined as a substance above its critical temperature (Tc) and pressure (Pc)1, but below the pressure required for condensation to a solid, see Figure 6.1 [1], The last requirement is often omitted since the pressure needed for condensation to occur is usually unpractically high. The critical point represents the highest temperature and pressure at which the substance can exist as a vapour and liquid in equilibrium. Hence, in a closed system, as the boiling point curve is ascended, increasing both temperature and pressure, the liquid becomes less dense due to thermal expansion and the gas becomes denser as the pressure rises. The densities of both phases thus converge until they become identical at the critical point. At this point, the two phases become indistinguishable and a SCF is obtained. 

The main comparisons between extraction methods have been made between the Soxhlet, ultrasonication, and supercritical fluid extraction [377, 398,456,461,462]. This has primarily been prompted by the need to evaluate critically the relative merits of SFE as an alternative to the more established methods. Richards and Campbell [456] made a comparison between SFE, Soxhlet, and sonication methods for the determination of some priority pollutants in soil. The SFE apparatus was the same, relatively standard system as described by Campbell et al. [457] with the addition of a C02 cryogenic trap to... 

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