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in the complete precipitation of any dissolved mate- rial, rendering product recovery easy. This may be true, but use of such a route for product recovery raises costs, as one must then either recompress the CO2 prior to re-use or compress make-up CO2. As gas compression is energy-intensive and expensive, a greener route to product recovery is desirable. One example of product recovery without a high- pressure drop is liquid–liquid extraction against water. A liquid–liquid extraction between an organic and aqueous phase inevitably cross-contaminates the phases, normally requiring remediation of one, and probably both phases. In the case of a water–CO2 ex- traction, however, the inevitable cross-contamination is benign (carbonated water!). Indeed, the CO2-based coffee decaffeination process employs a water–CO2 extraction to recover the caffeine, allowing the CO2 to move in loop at relatively constant pressure (see Fig. 3). Further, the cross-contamination here is actua- lly beneficial, as the low pH in the ‘CO2-contaminated’ water allows for a higher partition coefficient for caf- feine, while the ‘water-contaminated’ CO2 is a better extractant for caffeine than pure CO2. Beckman and Hancu also employed a liquid–liquid extraction, here for the recovery of H2O2 synthesized in CO2 [14]. 1.7.1.4. Operate the process continuously if possible. The rationale for operating in a continuous mode is that the equipment can be smaller while maintaining high productivity. While this is usually straightforward for liquid substrates, it can be much more difficult for the processing of solids at high pressure. Indeed, there currently does not exist a viable means for introducing and removing solids continuously from a high pressure (100 bar +) process. Those commercial CO2-based processes that employ solids use either batch or semi-batch mode. An example of the latter is the coffee decaffeination process, where dual extraction columns are employed, such that one is in extraction mode while the other is being emptied and re-filled [16]. In the late 1980s, Chiang et al. at the University of Pittsburgh developed a process (LICADO) for the cleaning of coal that employed a biphasic mixture of CO2 and water [44]. Here, the coal was introduced to the process continuously as a slurry in water. If the use of a water slurry of solid substrate is tolerable, this is a useful means by which to introduce solids continuously into a high-pressure process. A clever example of the use of phase behav- ior trends to accomplish continuous processing, as well as to recover products without large pressure E.J. Beckman / J. of Supercritical Fluids 28 (2004) 121–191 131 Fig. 3. Process schematic for coffee decaffeination using CO2 [1].PDF Image | Supercritical and near-critical CO2 in green chemical synthesis and processing
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