Supercritical and near-critical CO2 in green chemical synthesis and processing

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Supercritical and near-critical CO2 in green chemical synthesis and processing ( supercritical-and-near-critical-co2-green-chemical-synthesis )

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such that they exhibit high solubility in CO2. In ad- dition, those processes where CO2 is employed as the minor component (use of CO2 as a plasticizer in poly- mer processing, for example) are likely to be favored economically. Another aspect of this issue is reflected in the typi- cal phase behavior of compounds in CO2 (see Figs. 1 and 2). Note that in the typical phase diagram of a crystalline solid in CO2, an essentially pure solid phase exists in equilibrium with a solution. Given that the solid phase cannot be processed, one obviously makes use of the solution, where naturally CO2 is the major component. For the case of liquid–liquid phase behavior, a CO2-rich phase exists in equilib- rium with a substrate-rich phase. However, because CO2 has been shown to lower the viscosity of solu- tions substantially, one can actually pump and process the substrate rich phase. Further, one can operate at lower pressure in addition to at higher concentration. Consequently, it may be beneficial to employ systems where liquid–liquid phase behavior occurs rather than liquid solid. Efficient operation of a process is both economically favorable and more environmentally friendly. E.J. Beckman / J. of Supercritical Fluids 28 (2004) 121–191 129 Fig. 1. Solid-fluid phase behavior [1]: CO2–naphthalene. Fig. 2. Liquid–liquid phase behavior [1]: CO2–hexane.

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