Supercritical fluid technology reactions

Supercritical Fluid Technology Reactions Table 3 Heterogeneous catalytic reactions in supercritical solvents 2921... 

The two fluids most often studied in supercritical fluid technology, carbon dioxide and water, are the two least expensive of all solvents. Carbon dioxide is nontoxic, nonflammable, and has a near-ambient critical temperature of 31.1°C. CO9 is an environmentally friendly substitute for organic solvents including chlorocarbons and chloroflu-orocarbons. Supercritical water (T = 374°C) is of interest as a substitute for organic solvents to minimize waste in extraction and reaction processes. Additionally, it is used for hydrothermal oxidation of hazardous organic wastes (also called supercritical water oxidation) and hydrothermal synthesis. 

Over the past decade, much progress in supercritical fluid technology has occurred. For example, supercritical fluids have found widespread use in extractions (2-5), chromatography (6-9), chemical reaction processes (10,11), and oil recovery (12). Most recently, they have even been used as a solvent for carrying out enzyme-based reactions (14). Unfortunately, although supercritical fluids are used effectively in a myriad of areas, there is still a lack of a detailed understanding of fundamental processes that govern these peculiar solvents. 

We now turn attention to a completely different kind of supercritical fluid supercritical water (SCW). Supercritical states of water provide environments with special properties where many reactive processes with important technological applications take place. Two key aspects combine to make chemical reactivity under these conditions so peculiar the solvent high compressibility, which allows for large density variations with relatively minor changes in the applied pressure and the drastic reduction of bulk polarity, clearly manifested in the drop of the macroscopic dielectric constant from e 80 at room temperature to approximately 6 at near-critical conditions. From a microscopic perspective, the unique features of supercritical fluids as reaction media are associated with density inhomogeneities present in these systems [1,4],... 

More polymerization reactions carried out at supercritical conditions, select biomass conversion supercritical fluid technologies for hydrogen production, wider use of supercritical water oxidation processes, portfolio of self-assembly applications, a spate of opportunities in process intensification, many supercritical fluid aided materials synthesis applications, and numerous reactions for synthesis of specialty chemicals are expected for years to come. 

A variety of chemical and biological reactions involving supercritical fluid technology are being explored and developed. They include polymerization reactions, biomass conversion, hydrogen production, applications of supercritical water oxidation, self-assembly applications, synthesis of specialty chemicals, manufacture of materials with tailored properties, and much more. These developments and new ones are expected to mature and be commercially deployed in years to come. 

Hutchenson KW. Organic chemical reactions and catalysis in supercritical fluid media. In Sun Y-P, ed. Supercritical Fluid Technology in Materials Science and Engineering. New York Marcel Dekker, 2002 87-187. 

A chemical destruction method that has been used for the treatment of PCBs in contaminated dielectric liquids or soil is based on the reaction of a polyethylene glycol/potassium hydroxide mixture with PCBs (De Filippis et al. 1997). This method can be used successfully for the destruction of higher chlorinated PCBs with an efficiency of >99%, but was found to be unsuitable for the treatment of di- and trichlorobiphenyls due to low destruction efficiencies (Sabata et al. 1993). Irradiation of PCBs in isooctane and transformer oil by y-radiation resulted in degradation of PCBs to less chlorinated PCBs and PCB-solvent adducts (Arbon et al. 1996). Supercritical fluid technology has shown promise as a method for extraction of PCBs from soils, coupled with supercritical water oxidation of the extracted PCBs (Tavlarides 1993,1998a). Hofelt and Shea (1997) demonstrated the use of semipermeable membrane devices to accumulate PCBs from New Bedford Harbor, Massachusetts water. Another method showing... 

Based on the polarity difference between CO2 and the interior of the micelles, w/c microemulsions have found many applications as extraction media. Furthermore, by modifying pressure and temperature, solvent quality may be changed and it becomes, therefore, possible to exert a real control over the extraction process uptake of solutes inside micelles may be varied. This may be of use for separations/extractions involving bio-chemicals and proteins. In conventional solvents their separation from the reaction medium can be quite complicated, involving tedious processes such as fluid-fluid extraction, decantation, chromatography column, filtration, precipitation. Use of supercritical fluid technology with extraction in reverse micelles seems advantageous for proteins (e.g. 19, 76). This process was also used for the extraction of metals (77-79) and more recently of copper from a filter paper surface (1). 

As mentioned earlier, physical chemistry plays a significant role in providing understanding of phenomena important to developing supercritical fluid technology for chemical synthesis applications (see Figure 3). A previous study of Diels-Alder reactions with cyclopentadiene and ethyl acrylate in our group illustrates this important role. As mentioned above, of paramount interest was the intrinsic rate of this bimolecular reaction as well as the endo to exo selectivity in scCOa this... 

Welch, J.F. and Siegwarth, J.D. (1987) Destruction of Hazardous DOD Wastes by Chemical Reaction in a Supercritical Fluid, in R.D. Smith et al. (eds.). Supercritical Fluid Technologies Basic Research Needs for DOD Applications, U.S. Army Research Office Workshop Report. 

Overall, the book presents a relatively new and focused topic on supercritical fluid technology In enzymatic reaction system[s]. The writing style of the book has a good flow of information and [is] easy to understand. ... 

JR Combes, KP Johnston, KE O Shea, MA Fox. Influence of solvent-solute and solute-solute clustering on chemical reactions in supercritical fluids. In FV Bright, MEP McNally, eds. Supercritical Fluid Technology Theoretical and Applied Approaches to Analytical Chemistry. ACS Symposium Series No. 488. Washington, D.C. American Chemical Society, 1992, pp 31 7. 

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