Browsing by Author "Macedo, Maria E."
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- Application of the GCA-EoS model to the supercritical processing of fatty oil derivativesPublication . Ferreira, Olga; Macedo, Maria E.; Brignole, Esteban A.The group-contribution with association equation of state (GCA-EoS) is applied to represent high-pressure phase equilibria in mixtures of supercritical gases (carbon dioxide, propane) with fatty oil derivatives, such as mono- and di-glycerides, fatty acids and fatty acid esters. Association effects in these mixtures are described by a group-contribution approach using three different association groups: the hydroxyl group, the acid group and the ester group. Satisfactory predictions of vapor–liquid equilibria, liquid–liquid equilibria and c1 of binary and ternary mixtures of high-molecular weight triacyglycerides and their derivatives with carbon dioxide or propane are obtained. It is shown that the GCA-EoS is a powerful engineering tool for the design and optimization of extraction and fractionation processes of fatty oil derivatives with supercritical fluids.
- Effectiveness factor for immobilized biocatalysts: two substratestwo products reactionsPublication . Ribeiro, Adriano S.; Ferreira, Olga; Macedo, Maria E.; Loureiro, José M.Immobilized enzymes are being increasingly used as biocatalysts in numerous processes to obtain high-value products for the pharmaceutical, flavour and fragrance industries (Gandhi et al., 2000). The major advantages of immobilization include the increase in enzyme stability, the possibility of enzyme reutilization and the easy separation of the biocatalysts from the reaction mixture. However, it is necessary to account for mass transfer limitations that, under some conditions, may arise in these systems (Gómez et al., 2003; Jeison et al., 2003). These resistances comprise the effects of intraparticle diffusion and external mass-transfer. Given the complexity of the kinetics of multisubstrate enzyme reactions, reactor modelling studies that account for mass-transfer phenomena are so far limited to single-substrate ones (Gómez et al., 2003). To compare the observed reaction rate with the reaction rate in the absence of mass-transfer limitations, an overall effectiveness factor is usually calculated (Gómez et al., 2003; Jeison et al., 2003). In this work, a model is developed to calculate the overall effectiveness factor for immobilized enzymes that carry out irreversible two substrates-two products reactions following kinetic mechanisms such as the Ternary Complex or the Ping-Pong Bi-Bi with inhibition by the second substrate. The model has two dimensionless parameters for each substrate – Thiele modulus (reaction/intraparticle diffusion), Biot number (film diffusion/intraparticle diffusion) – and one related to the reaction kinetics. Their influence on the effectiveness factor is analysed. The results obtained can be applied in the design and simulation of enzymatic reactors.
- Extension of the A-UNIFAC model to mixtures of cross- and self-associating compoundsPublication . Ferreira, Olga; Macedo, Maria E.; Bottini, Susana B.In the present work an extended UNIFAC group contribution model is used to calculate activity coefficients in solutions containing alcohols, water, carboxylic acids, esters, alkanes and aromatic hydrocarbons. The limiting expressions for the association contribution to the activity coefficients at infinite dilution are presented and discussed. A new set of interaction parameters between associating and non-associating functional groups is reported. This set of parameters is applied in the association model to predict vapor–liquid, liquid–liquid equilibrium and infinite dilution activity coefficients.
- Modelling of phase equilibria for associating mixtures using an equation of statePublication . Ferreira, Olga; Brignole, Esteban A.; Macedo, Maria E.In the present work, the group contribution with association equation of state (GCA-EoS) is extended to represent phase equilibria in mixtures containing acids, esters, and ketones, with water, alcohols, and any number of inert components. Association effects are represented by a group-contribution approach. Self- and cross-association between the associating groups present in these mixtures are considered. The GCA-EoS model is compared to the group-contribution method MHV2, which does not take into account explicitly association effects. The results obtained with the GCA-EoS model are, in general, more accurate when compared to the ones achieved by the MHV2 equation with less number of parameters. Model predictions are presented for binary self- and cross-associating mixtures.
- Phase equilibria in sugar solutions using the A-UNIFAC modelPublication . Ferreira, Olga; Brignole, Esteban A.; Macedo, Maria E.In this work, a modified UNIFAC model that explicitly takes into account association effects is used to describe the thermodynamic properties of phase equilibria of mixtures containing common sugars, alcohols, and water. Three main groups were defined to represent the sugars family: the sugar ring (pyranose and furanose), the osidic bond (-O-), and the hydroxyl ring group (OHring). For the association term, a general two-site OH associating group is used to represent association effects in these solutions, allowing a straightforward extension to multicomponent mixtures. Correlation of both solvent properties (osmotic coefficients, water activities, vapor pressures, and boiling and freezing points of binary aqueous sugar solutions) and sugar solubility in water and alcohols gives very accurate results. Good predictions are obtained for vapor-liquid equilibrium and solid-liquid equilibrium of ternary and quaternary mixtures of sugars in mixed solvents.