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1.2 Strategic Organic Solvent Replacement Solvents that have interesting potential as environmentally benign alternatives to organic solvents include water, ionic liquids, fluorous phases, and supercriti- cal or dense phase fluids [5, 6]. Obviously, each of these approaches exhibits specific advantages and potential drawbacks. Ionic liquids (room-temperature molten organic salts), for example, have a vapor pressure that is negligible. Be- cause they are non-volatile, commercial application would significantly reduce the VOC emission. In general, ionic liquids can be used in existing equipment at reasonable capital cost [7]. Nevertheless, the cost of a room-temperature mol- ten salt is substantial. In addition, the separation of ionic liquids from a process stream is another important point of concern. With respect to dense phase fluids, supercritical water has been shown to be a very effective reaction medium for oxidation reactions [8, 9]. Despite extensive research efforts, however, corrosion and investment costs form major challenges in these processes because of the rather extreme operation conditions required (above 647 K and 22.1 MPa) [10]. Still, several oxidation processes for waste water treatment in chemical industries are based on supercritical water technol- ogy (see, e.g., [11]). In Table 1.1, the critical properties of some compounds which are commonly used as supercritical fluids are shown. Of these, carbon dioxide and water are the most frequently used in a wide range of applications. The production of polyethylene in supercritical propane is described in a loop reactor [13]. Super- critical ethylene and propylene are also applied, where they usually act both as a solvent and as the reacting monomer. In the field of polymer processing, the Dow Chemical Company has developed a process in which carbon dioxide is used to replace chlorofluorocarbon as the blowing agent in the manufacture of polystyrene foam sheet [14, 15]. Table 1.1 Critical conditions of several substances [12]. 1.2 Strategic Organic Solvent Replacement 3 Solvent Acetone Ammonia Carbon dioxide Cyclohexane Diethyl ether Difluoromethane Difluoroethane Dimethyl ether Ethane Ethylene Ethyne Tc (K) 508.1 405.6 304.1 553.5 466.7 351.6 386.7 400.0 305.3 282.4 308.3 Pc (MPa) 4.70 11.3 7.38 4.07 3.64 5.83 4.50 5.24 4.87 5.04 6.14 Solvent Hexafluoroethane Methane Methanol n-hexane Propane Propylene Sulfur hexafluoride Tetrafluoromethane Toluene Trifluoromethane Water Tc (K) 293.0 190.4 512.6 507.5 369.8 364.9 318.7 227.6 591.8 299.3 647.3 Pc (MPa) 3.06 4.60 8.09 3.01 4.25 4.60 3.76 3.74 41.1 4.86 22.1PDF Image | Supercritical Carbon Dioxide for Sustainable Polymer Processes
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