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solvent, yet equivalent attention must be paid to the monetary ‘green’ as to the sustainable ‘green’ to cre- ate commercially successful processes that use CO2. Acknowledgements The author wishes to acknowledge the financial sup- port of the US Environmental Protection Agency (Req- uisition/Reference No.: TM1150 QT-DC-01-001351; State of the Science Report) during the preparation of this paper. The author further wishes to thank Barb Karn and Ted Just at the US EPA for their support dur- ing creation of this manuscript and a variety of staff at the US EPA for reviewing this paper. Finally, it is always difficult to prepare a review that covers all of the relevant science and hence the author wishes to thank Dr J. DeSimone, Dr J. Brennecke, Dr B. Knut- son, Dr P. Jessop, Dr S. Howdle, Dr. M. Abraham, and Dr C. Roberts for their extremely helpful comments and suggestions. References [1] (a) M.A. McHugh, V.J. Krukonis, Supercritical Fluid Extraction, second ed, Butterworth-Heinemann, Boston, MA, 1994; (b) G. Brunner, Gas Extraction, Steinkopff Verlag, Darmstadt, Germany, 1994. [2] (a) A. Michels, C. Michels, Proc. Roy. Soc. (Lond.) A 153 (1936) 201; (b) A. Michels, C. Michels, H. Wouters, Proc. Roy. Soc. (Lond.) A 153 (1936) 214. [3] S. Angus, B. Armstrong, K.M. de Reuck, Carbon Dioxide (On the basis of surveys and equations produced by V.V. Altunin) Oxford University Press, New York, 1976. [4] (a) J.C. Giddings, M.N. Myers, L. McLaren, R.A. Keller, Science 162 (1969) 67; (b) J.C. Giddings, M.N. Myers, J.W. King, J. Chromatogr. Sci. 7 (1969) 276. [5] (a) Praxair Material Data Safety Sheet, P-4574-H, May, 1999; (b) D.R. Lide, (Ed.), CRC Handbook of Chemistry and Physics, seventy-sixth ed., CRC, Boca Raton, FL, 1996, Chapter 16. [6] B. Minder, T. Mallat, A. Baiker, Third International Sym- posium on High-Pressure Chemical Engineering, Zurich, 1996, p. 139. [7] (a) F. Solymosi, E. Erdohelyi, M. Lancz, J. Catal. 95 (1985) 567; (b) A. Erdohelyi, M. Pasztor, F. Solymosi, J. Catal. 98 (1986) 106. [8] (a) L.W. Lake, Enhanced Oil Recovery, Prentice Hall, Englewood Cliffs, NJ, 1989; (b)A. Chakma, M.R. Islam, F. Berruti (Eds.), Enhanced Oil Recovery, Am. Inst. Chem. Eng. Symp. Ser. 280, New York, 1991. [9] J.O. Pande, J. Tonheim, Proc. Safety Progr. 20 (2001) 37. [10] D.J. Van Bramer, M.B. Shiflett, A. Yokozeki, US Patent 5,345,013, 1994. [11] F. Rodriguez, Principles of Polymer Systems, fourth ed, McGraw-Hill, New York, 1996. [12] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Liquids and Gases, fourth ed, McGraw-Hill, New York, 1987. [13] K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, third ed, Wiley, VCH-Weinheim, Germany, 1997. [14] D. Hancu, E.J. Beckman, Green Chem. 3 (2001) 80. [15] C.A. Eckert, C.L. Liotta, C.W. Culp, D.R. Lamb, in: P.G. Jessop, W. Leitner (Eds.), Chemical Synthesis Using Super- critical Fluids, Wiley VCH, Weinheim, Germany, 1999, p. 446. [16] (a) K. Zosel, US Patent No. 3,806,619, 1974, April 23; (b) R. Prasad, M. Gottesman, R.A. Scarella, US Patent No. 4,246,291, 1981, Jan. 20. [17] J.L. Kendall, D.A. Canelas, J.L. Young, J.M. DeSimone, Chem. Rev. 99 (1999) 543. [18] (a) J.M. Tanko, J.F. Blackert, Science 263 (1994) 203; (b) S. Hadida, M.S. Super, E.J. Beckman, D.P. Curran, J. Am. Chem. Soc. 119 (1997) 7406. [19] C.Y. Tsang, W.B. Street, Chem. Eng. Sci. 36 (1981) 993. [20] Y.-L. Hsiao, J.M. DeSimone, J. Polym. Sci. Part A: Polym. Chem. 35 (1997) 2009. [21] C.A. Eckert, Presentation at the International Symposium on Supercritical Fluid Technology, Myrtle Beach, SC, August 18–23, 2001. [22] The convective heat transfer flux is proportional to the heat transfer coefficient (h), where h is correlated to physical properties through a correlation of the form h = k(Re)x (Pr)y where Pr (the Prandtl number) = μCp/k and Re (the Reynolds number) = ρDv/. Here μ is the viscosity, ρ is the density, ν the fluid velocity, k the thermal conductivity and Cp the heat capacity. For the case of natural convection (convection induced by temperature gradients in the fluid), the heat transfer coefficient correlates with the thermal conductivity, the Prandtl number and the Grashof number (Gr), where Gr = βgρ2D3T/μ2; where T is the temperature difference between the surface and the fluid, while β is the coefficient of thermal expansion. See, for example, J.R. Welty, C.E. Wicks, R.E. Wilson, Fundamentals of Momentum, Heat, and Mass Transfer, third ed., Wiley and Sons, New York, 1984. [23] (a) S. Inoue, N. Yamazaki, Organic and Bioorganic Chemis- try of Carbon Dioxide, Wiley and Sons, New York, 1982; (b) K.N. West, C. Wheeler, J.P. McCarney, K.N. Griffith, D. Bush, C.L. Liotta, C.A. Eckert, J. Phys. Chem. A 105 (2001) 3947. [24] A.J. Mesiano, E.J. Beckman, A.J. Russell, Chem. Rev. 99 (1999) 623. E.J. Beckman / J. of Supercritical Fluids 28 (2004) 121–191 183PDF Image | Supercritical and near-critical CO2 in green chemical synthesis and processing
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