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400 350 300 250 200 CO2 Pext Psep 4.4 librium Problems”, Ber. Bunsen-Ges. Phys. Chem., 88, 801-806 (1984). Brunner, G., “Design and Scale-up of Processes with Supercritical Fluids: The Solvent Cycle”, 5th Inter- national Symposium on Supercritical Fluids Westin Atlanta North Atlanta, USA, April 8-12 (2000). Brunner, G., Gas Extraction. An Introduction to Fun- damentals of Supercritical Fluids and the Applica- tion to Separation Processes, Springer, NY (1994) Budich, M., S. Heilig, T. Wesse, V. Leibkuchler and G. Brunner, “Countercurrent Deterpenation of Citrus Oil with Supercritical CO2”, J. Supercritical Fluids, 14, 105-114 (1999). Diaz, S. and J.A. Bandoni, “A Mixed Integer Optimiza- tion Strategy for a Large Scale Plant in Operation”, Comp. Chem. Eng., 20, 5, 531-545 (1996). Diaz, S., S. Espinosa and E.A. Brignole,. “Modeling and Simulation Tools for Supercritical Fluid Processes”, Computer Aided Process Eng., 8, 319-324 (2000). Duran, M. and I.E. Grossmann, “A Mixed-Integer Non- linear Programming Approach for Process Systems Synthesis”, AIChE J., 32, 592-606 (1986). Espinosa, S., S. Diaz and E.A. Brignole, “Optimal De- sign of Supercritical Fluid Processes Comp. Chem. Eng., 24, 2/7, 1301-1307 (2000). Institut Français du Pétrole, Manual of Economic Analy- sis of Chemical Processes. McGraw-Hill Book Company, France (1981). Kalra, H., S.Y.-K Chung, and C.-J. Chen, “Phase Equi- librium Data for Supercritical Extraction of Lemon Flavors and Palm Oils with Carbon Dioxide”, Fluid Phase Equilibria, 36, 263-278 (1987). Marteau, Ph., J. Obriot and R. Tufeu, “Experimental Determination of Vapor-Liquid Equilibria of CO2 + Limonene and CO2 + Citral Mixtures”, J. Supercriti- cal Fluids, 8, 20-24 (1995). Michelsen, M.L., “The Isothermal Flash Problem. Part II. Phase Split Calculation”, Fluid Phase Equilibria, 9, 21-40 (1982). Pusch, J. and J. Schmelzer, “Extension of the Group- Contribution Equation of State Parameter Matrix for the Prediction of Phase Equilibria Containing Argon, Ammonia, Propene and other Alkenes”, Ber. Bun- senges. Phys. Chem., 97, 597-603 (1993). Schrage, L. Linear, Integer and Quadratic Program- ming With LINDO. The Scientific Press, Palo Alto (1987). Skjold-Jørgensen, S., “Gas Solubility Calculations. II. Application of a New Group-Contribution Eqn. of State”, Fluid Phase Equilibria, 16, 317-351 (1984) Ulrich G.D., A Guide to Chemical Engineering Process Design and Economics, John Wiley & Sons, (1984). Received: September 16, 2001. Accepted for publication: November 06, 2002. Recommended by Guest Editors: J. Cerdá and A. Bandoni. 2.6 2.8 Figure 7. T-S diagram for CO2 recycle. V. CONCLUSIONS C P P: pump mode work C: compressor mode work 3.0 3.2 3.4 3.6 3.8 4.0 4.2 Entropy (KJ/Kg K) The problem of optimal solvent cycle design has been addressed as an MINLP problem for the supercritical deterpenation of lemon oil. Argentina is lemon first world producer and a nontoxic technology for the pro- duction of a high commercial value aroma, as citral seems to be of great interest. The MINLP model in- cludes reliable thermodynamic predictions with a Group Contribution Equation of State and rigorous unit mod- els. The close agreement between experimental equilib- rium and solubility data for the ternary system li- monene-citral-CO2 and thermodynamic predictions, together with rigorous process simulation models guar- antee optimal process schemes and operating condi- tions. A better insight has been obtained as regard proc- ess feasibility, operating conditions and solvent cycle design when performing economic evaluation through a detailed cost analysis. Acknowledgements The authors gratefully acknowledge financial support from CONICET, ANPCYT and Universidad Nacional del Sur, Argentina. REFERENCES Bamberger, A., J. Schmelzer, D. Walther and G. Mau- rer, “High-Pressure Vapour-Liquid Equilibria in Bi- nary Mixtures of Carbon Dioxide and Benzene Compounds and their Correlation with the General- ized Bender and Skjold-Jorgensen's Group Contri- bution Equation of State”, Fluid Phase Equilibria, 97, 167-189 (1994). Biegler, L. And J. Cuthrell, “Improved Infeasible Path Optimization for Sequential Modular Simulators.II: The Optimization Algorithm”, Comp. Chem. Eng. 9, 257-267 (1985). Brignole, E.A., P.M. Andersen and Aa. Fredenslund, “Supercritical Fluid Extraction of Alcohols from Water”, Ind. Eng. Chem. Res. , 26, 254-261 (1987). Brignole, E.A., S. Skjold-Jorgensen and Aa. Fre- denslund, “Application of a Local Composition Equation of State to Supercritical Fluid Phase Equi- M. S. DIAZ, S. ESPINOSA, E. A. BRIGNOLE Temperature (K) 165PDF Image | SOLVENT CYCLE DESIGN IN SUPERCRITICAL FLUID PROCESSES
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