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182 E.J. Beckman / J. of Supercritical Fluids 28 (2004) 121–191 implications of a narrowly focused study published previously. 7. Areas for future research on CO2 technology In each of the previous sections, mention has been made of potentially useful avenues for future research; these will be summarized below (in no particular or- der). • The use of biphasic systems (including carbon dioxide as one component) for conducting reactions using gaseous components. • A greater focus on oxidations and hydroformy- lations, versus hydrogenation in CO2; the former reactions generate more waste and require more stringent conditions than hydrogenation, yet have received relatively less attention in the literature (with respect to the sub-field of reactions in CO2). • Group contribution or better yet, first principles models for the prediction of phase behavior in multi-phase, multi-component systems where car- bon dioxide is one of the components. Prediction of basic transport properties is needed as well. In order to do this, one needs a fundamental under- standing of the effects of chemical structure and topology on the phase behavior of molecules in carbon dioxide; this should also result in the design of ‘CO2-philes’ that do not include fluorine. • An understanding of the fundamentals behind sol- vation of hydrophilic compounds (including water) in CO2 -based emulsions; also thermodynamics and transport properties of the CO2 –water interface. This would address the frustrating observation that not all CO2 -soluble amphiphiles can solubilize water. • The design of equipment that would allow rapid injection and removal of solids from high pressure, CO2-rich environments. Also, the design of systems for the rapid high-pressure treatment of solid arti- cles (as in the development of silicon wafers) or the continuous coating of material using a CO2-based solution. Such work would benefit diverse CO2 ap- plications, including microelectronics processing, the dyeing of textiles, cleaning and extraction. • The use of CO2 in microelectronics processing. This is an application where concurrent design at the molecular and process level is needed. • An in-depth understanding of the mechanism for generation of CO and subsequent poisoning of no- ble metal catalysts in the presence of hydrogen and CO2 and hence, the design of catalysts that can effectively perform hydrogenations for extended time periods in carbon dioxide. • The design of catalysts for the generation of poly- esters and commodity chemicals (aromatic acids) from CO2; activation of CO2 at low pressures. • Also, IT would be useful to explore the use of co- solvents for CO2 in a more systematic manner, to find mixtures that are technically, environmen- tally and economically successful. The use of ‘expanded’ solvents in reactions is included here. • The design of additives that would allow greater use of CO2 in the extrusion foaming of polymers. Also, the generation of low density, fine-celled foams using CO2 as the blowing agent. • The development of a set of fundamental design principles for the formation of particles via phase separation from mixtures that include CO2 (under flow in a known geometry). • Programs that focus on overcoming the various technical hurdles to the use of CO2 in coating processes. For example, while problems in using CO2 to process powder coating formulations differ greatly from problems encountered in preparing emulsion coating formulations using CO2 , the problems are inherently technical in nature. • Identification of applications where CO2 might re- place water, whose use in arid climates is not always sustainable. These include fabric dyeing, cleaning and microelectronics processing—are there others? Whether one agrees with these areas of emphasis or not, the list shown above reveals that while the use of carbon dioxide as a solvent as part of a green process- ing scheme might be considered (in 2002) a relatively mature technology, it remains a rich area for future re- search. Further, while use of carbon dioxide is often prompted by environmental concerns, recent commer- cialization efforts show that use of CO2 in a process can provide product quality and safety advantages as well as enhanced sustainability. Successful commer- cial implementations of CO2 -based technology show clearly that a close collaboration between scientists and engineers is needed to bring promising ideas to fruition. Carbon dioxide is without question a benignPDF Image | Supercritical and near-critical CO2 in green chemical synthesis and processing
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