Phase Equilibria of CO2-Based Reaction Systems

摘要圣母大学琼·F·布伦内克大学CTS-9522835超临界(SC)二氧化碳已被证明是一种可行的反应介质，可用于各种反应。例如，最近的研究表明，商业上重要的过程，如前手性烯烃和酮的不对称氢转移氢化和环己烯氧化为己二酸，都可以在超临界二氧化碳中进行。在二氧化碳中操作的好处在于它有可能取代危险的有机溶剂(特别是氯化溶剂)。由于无毒，一些反应速度在超临界二氧化碳中实际上是加速的，有一些例子表明，使用二氧化碳作为溶剂还可以对所需化合物产生更好的选择性，并且超临界流体中的溶解度可调建议了可能的节能下游分离方案。因此，超临界二氧化碳中的化学反应和加工是传统制造技术的一个有吸引力的替代方案。

ABSTRACT Joan F. Brennecke University of Notre Dame CTS-9522835 Supercritical (SC) carbon dioxide has been shown to be a viable reaction medium for a wide variety of reactions. For example, it has recently been shown that commercially important processes, such as the asymmetric hydrogen-transfer hydrogenation of prochiral olefins and ketones and the oxidation of cyclohexene to adipic acid, can be run in supercritical carbon dioxide. The benefit of operation in CO2 lies in its potential for replacing hazardous organic solvents (chlorinated solvents, in particular). Being non-toxic, some reaction rates are actually accelerated in SC CO2, there are some examples in which the use of CO2 as the solvent also results in better selectivity for the desired compound, and the tunability of solubilities in supercritical fluids suggests possible energy-saving downstream separation schemes. Thus, chemical reaction and processing in SC CO2 is an attractive alternative to conventional manufacturing techniques.