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Mixed Integer Nonlinear Programming (MINLP) model: ables y have been associated to potential units in the process and the solvent recovery system. Equality con- straints, h, represent the process mathematical model. It is solved within a sequential process simulator which includes rigorous models for a high-pressure multistage extractor (Brignole et al., 1987) and a multiphase flash (Michelsen, 1982). The GC-EOS has been integrated as thermodynamic support for these model unit simulation routines. Additional equality constraints c correspond to reflux recycle, as the nonlinear optimization subproblem has been solved in an infeasible-path way. Inequality constraints, g, include product purity and recovery specifications, solvent purity and operating bounds. Max f(x,y) x,y s.t. h(x,y) = 0 c(x)=0 g(x,y) ≤ 0 x ε Rn, xL ≤ x ≤ xU, y ε {0,1}m where vector x corresponds to continuous optimization variables: extraction pressure, solvent recovery unit pressure, solvent flowrate and reflux ratio. Binary vari- M. S. DIAZ, S. ESPINOSA, E. A. BRIGNOLE y5=1 y6=1 CO2 C1 y1=1 C2 y2=1 CO2 S2 natural lemon oil limonene concentrate E HE3 y3=1 HE1 CO2 y4=1 make-up CO2 S3 citral concentrate P1 HE2 Figure 6. Supercritical deterpenation scheme with solvent cycle superstructure Figure 6 shows the deterpenation process together with the solvent recovery system superstructure. In the extraction column (E), lemon oil is fed at the sixth stage in countercurrent with supercritical carbon dioxide; citral is the raffinate. Limonene and carbon dioxide con- stitute the extract, which may be heated (y5=1) and/or expanded through a Joule-Thomson valve (y6=1) to re- duce solute solubility in supercritical carbon dioxide. This stream is then sent to a solvent recovery unit (S1); the vapor is the recovered solvent and the liquid is partly returned to the extractor as reflux and partly re- covered as limonene product after a further expansion to ambient pressure. Other alternative to separate the ex- tract from the solvent is to change temperature in order to reduce solute solubility in carbon dioxide at constant pressure, so the valve (V1, y6=1) is also optional; how- ever solvent purity for reuse cannot be achieved in this option. In compression mode, the recovered carbon di- oxide is compressed (C1, centrifugal, y1=1 or C2, recip- rocal, y2=1) to extraction pressure and then it is cooled to extraction temperature (HE1, y3=1). In pumping mode (y4=1), the recovered solvent is condensed (HE2), pumped (P1) and heated (HE3) to extraction pressure and temperature respectively. In pumping mode, a pro- pane refrigeration cycle has been considered to con- dense carbon dioxide; the solvent is heated in HE3 with low-pressure steam to extractor temperature. In com- pressor mode, the solvent is cooled (HE1) to extractor temperature with cooling water. The objective is to maximize net profit. 163 S1PDF Image | SOLVENT CYCLE DESIGN IN SUPERCRITICAL FLUID PROCESSES
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