Liquids processing, with supercritical

Separation processes with supercritical gases, called supercritical fluid extraction (SFE), is a group of separation processes that applies supercritical fluids (SCFs) as separating agents in the same way as other separation processes, such as liquid-liquid extraction or absorption, make use of liquid solvents. In these processes, the solvent is a supercritical component or a supercritical mixture of components [1-3]. 

Fractionation of liquid mixtures with supercritical carbon dioxide in counter-cur-rent columns can be operated continuously, because liquids can be easily pumped into and out of a column. This represents a big advantage over extrachon from solid materials, as it allows real process intensification - large quantities of feed can be processed with only a small volume under high pressure at any given time. Frac-tionahon, mostly of natural products or extracts, has been extensively studied at the laboratory and pilot-plant scale. The design principles of this type of column have been established, and scale-up procedures devised [1,6]. They can be operated with reflux, as in distillation, and frachonahon can therefore become an extremely se-lechve process. Difficult separahons can be effechvely carried out. 

It is for these reasons the replacement of volatile organic solvents (VOCs) in homogeneous cataljdic processes with supercritical CO (Sc-CO ) has received considerable attention. The supercritical state of carbon dioxide is reached at 30.95 C and 72.8 atm pressures at which point the phase boundary between the liquid and gaseous phases disappears. After this point, temperature and/or pressure can be increased without effecting any phase change. 

Catalysis in a single fluid phase (liquid, gas or supercritical fluid) is called homogeneous catalysis because the phase in which it occurs is relatively unifonn or homogeneous. The catalyst may be molecular or ionic. Catalysis at an interface (usually a solid surface) is called heterogeneous catalysis, an implication of this tenn is that more than one phase is present in the reactor, and the reactants are usually concentrated in a fluid phase in contact with the catalyst, e.g., a gas in contact with a solid. Most catalysts used in the largest teclmological processes are solids. The tenn catalytic site (or active site) describes the groups on the surface to which reactants bond for catalysis to occur the identities of the catalytic sites are often unknown because most solid surfaces are nonunifonn in stmcture and composition and difficult to characterize well, and the active sites often constitute a small minority of the surface sites. 

When ionic liquids are used as replacements for organic solvents in processes with nonvolatile products, downstream processing may become complicated. This may apply to many biotransformations in which the better selectivity of the biocatalyst is used to transform more complex molecules. In such cases, product isolation can be achieved by, for example, extraction with supercritical CO2 [50]. Recently, membrane processes such as pervaporation and nanofiltration have been used. The use of pervaporation for less volatile compounds such as phenylethanol has been reported by Crespo and co-workers [51]. We have developed a separation process based on nanofiltration [52, 53] which is especially well suited for isolation of nonvolatile compounds such as carbohydrates or charged compounds. It may also be used for easy recovery and/or purification of ionic liquids. 

The same types of catalyst have been employed in 1-octene hydroformylation, but with the substrates and products being transported to and from the reaction zone dissolved in a supercritical fluid (carbon dioxide) [9], The activity of the catalyst is increased compared with liquid phase operation, probably because of the better mass transport properties of scC02 than of the liquid. This type of approach may well reduce heavies formation because of the low concentration of aldehyde in the system, but the heavies that do form are likely to be insoluble in scC02, so may precipitate on and foul the catalyst. The main problem with this process, however, is likely to be the use of high pressure, which is common to all processes where supercritical fluids are used (see Section 9.8). 

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. 

An even more useful property of supercritical fluids involves the near temperature-independence of the solvent viscosity and, consequently, of the line-widths of quadrupolar nuclei. In conventional solvents the line-widths of e. g. Co decrease with increasing temperature, due to the strong temperature-dependence of the viscosity of the liquid. These line-width variations often obscure chemical exchange processes. In supercritical fluids, chemical exchange processes are easily identified and measured [249]. As an example. Figure 1.45 shows Co line-widths of Co2(CO)g in SCCO2 for different temperatures. Above 160 °C, the line-broadening due to the dissociation of Co2(CO)g to Co(CO)4 can be easily discerned [249]. 

In mercury speciation studies, pressurized liquid extraction (PLE), microwave-assisted extraction (MAE), and supercritical fluid extraction (SEE) are employed [33]. In particular, methyl-mercury is extracted by the Westoo method [33,34], which consists in a leaching process with hydrochloric acid, the extraction of the metal chloride into benzene or toluene, the addition of ammonium hydroxide that converts the metal species to hydroxide and the saturation with sodium sulfate. Most of the HPLC methods reported in literature for the determination of organomercury compounds (mainly monomethyhnercury, monoethyhnercury, and monophenylmercury) are based on reversed... 

This chapter covers the recent advances in amidocarbonylations, cyclohydrocarbonylations, aminocarbonylations, cascade carbonylative cyclizations, carbonylative ring-expansion reactions, thiocarbonylations, and related reactions from 1993 to early 2005. In addition, technical development in carbonylation processes with the use of microwave irradiation as well as new reaction media such as supercritical carbon dioxide and ionic liquids are also discussed. These carbonylation reactions provide efficient and powerful methods for the syntheses of a variety of carbonyl compounds, amino acids, heterocycles, and carbocycles. 

The PCA process uses supercritical fluid drying to help preserve fine microstructures in the material. Supercritical fluid drying is a technique that has been used for many years to dry biological materials and, more recently, aerogels (qv). The original solvent is replaced by exchange with a supercritical fluid, such as C02, and the system is depressurized above the critical temperature of the SCF. SCFs have no vapor—liquid interface. Thus fine microstructures are... 

Extraction of hops can also be achieved under liquid conditions (preferably 72 bar, 20°C) with production costs about 10% lower compared to the process with the supercritical condition (extraction pressure 350 bar, separation pressure 45 bar). However, because hops-extraction plants are operated only four to six months/year, extractions under supercritical conditions are preferred, as such a design provides more flexibility, by allowing the processing of other materials such as tea or cocoa... 

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