Papers by Esteban Brignole
The Journal of Supercritical Fluids
Abstract Conventional liquid extraction is not a suitable separation method for the recovery and ... more Abstract Conventional liquid extraction is not a suitable separation method for the recovery and dehydration of ethanol and other light alcohols from aqueous solutions. Condensed non-polar gases like propane and CO2 looked promising as potential solvents. The favorable effect of temperature on the alcohol distribution coefficient of condensed propane led to the development of the hot propane process (HPP) for extraction and dehydration of alcohols. The dehydration of the alcohols took place in the solvent recovery column, thanks to the water entrainment effect of propane. Earlier pilot plant studies confirmed the process feasibility. In the present work, we design mixtures of propane + CO2 and phase conditions that fulfill the key properties of the HPP: 1) good alcohol distribution coefficient in the high-pressure extractor and 2) adequate water entrainment effect in the solvent recovery column.
Latin American Applied Research, 2003
−− −− −− This work addresses the determination of optimal solvent cycle scheme for supercritical ... more −− −− −− This work addresses the determination of optimal solvent cycle scheme for supercritical fluid processes. The optimization model, which includes reliable thermodynamic predictions and rigorous process models, has been extended to include potential units that constitute the solvent recovery cycle. Capital cost functions, based on graphical correlations from the literature, have been derived for each unit in the superstructure. A mixed integer nonlinear programming model has been formulated, where the objective function is net profit maximization. Process and solvent cycle design has been performed for the deterpenation of lemon peel oil.
This work addresses modeling, simulation and optimization of countercurrent deterpenation of oran... more This work addresses modeling, simulation and optimization of countercurrent deterpenation of orange peel oil, modeled as a model mixture of limonene-linalool, with supercritical carbon dioxide as solvent. Binary and ternary systems are modeled with a group contribution equation of state, and vapor-liquid equilibria and selectivity predictions are compared to experimental data from different sources. A nonlinear programming model is proposed for the maximization of net profit. Process simulations are carried out at conditions reported in the literature and component purity and recovery in the output streams are contrasted against laboratory-scale process results. Optimization results provide operating conditions and equipment size to maximize net profit.Fil: Espinosa, Susana Noemi. Universidad Nacional del Comahue; ArgentinaFil: Díaz, María Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Brignole, Esteban Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentin
Journal of Chemical & Engineering Data, 2017
Heterogeneous catalytic gas−liquid reactions are intensified when carried out in the homogeneous ... more Heterogeneous catalytic gas−liquid reactions are intensified when carried out in the homogeneous fluid phase by means of a supercritical cosolvent. For instance, supercritical propane is used to enhance the yield in hydrogenation of vegetable oils. Besides phase equilibrium knowledge, volumetric information is also needed to elucidate kinetic mechanisms and design continuous supercritical reactors. In this work, we report new experimental PvT data on the reactive mixture H 2 + sunflower oil + propane using the isochoric method. In addition, the phase equilibria and PvT data are modeled with the GCA and RK−PR equations of state, respectively. The isochoric method provides not only PvT information under the reaction conditions but also the reactive system compressibility, which is a key variable to attain enhanced transport properties in supercritical reactors.
Separation and Purification Technology, 2016
Chelidonium majus L. is rich in many isoquinoline alkaloids which are responsible for the antiinf... more Chelidonium majus L. is rich in many isoquinoline alkaloids which are responsible for the antiinflammatory, antitumor and cytotoxic bioactivities known for this plant. The main alkaloids identified in C. majus L. include chelidonine, berberine, coptisine, sanguinarine and chelerythrine, which are present in different parts of the plant. In this work, alkaloids from C. majus aerial and terrestrial parts were extracted using a two step extraction procedure which consisted in a first step (SFE) using only supercritical carbon dioxide (scCO 2) as solvent followed by a second step (ESE) using scCO 2 and a co-solvent mixture composed by an alcohol (ethanol or isopropanol) and diethylamine (alkaline conditions). The effect of operation temperature, pressure, solvent density and solvent pH on extraction yields, kinetic profiles and alkaloids' selectivity was evaluated. Results showed that SFE presents high selectivity for alkaloids (particularly for chelidonine) at solvent densities in the range 813-850 kg/m 3 and for both the aerial and terrestrial parts of the plant. The highest alkaloids extraction yield was observed at higher solvent density conditions using the scCO 2 /isopropanol/diethylamine mixture (ESE extraction step). Chelidonine was found to be highly soluble in scCO 2. Therefore, the fractioned high pressure extraction procedure proposed in this work can be successfully applied to separate enriched chelidonine fractions, while other alkaloids can be obtained using basified isopropanol as co-solvent. This procedure demonstrates that alkaloids fractionation during extraction is an important tool to be used before further purification/isolation steps.
ACS Symposium Series, 1997
The Journal of Supercritical Fluids, 2002
... Author Keywords: Phase equilibria; Thermodynamic modeling; Group contribution; Triglycerides;... more ... Author Keywords: Phase equilibria; Thermodynamic modeling; Group contribution; Triglycerides; Vegetable oils. ... the calculation of both, the attractive energy parameter (a) and the co-volume (b), in ... However, it was not possible to correlate the VLE and LLE data using the same ...
The Journal of Supercritical Fluids, 2009
This review summarizes the advances made in the last decade in understanding the effect of phase ... more This review summarizes the advances made in the last decade in understanding the effect of phase conditions in the performance of supercritical reactors and in the control of process outputs. The study covers heterogeneous-catalyzed and non-catalytic supercritical reactions and shows the experimental and modeling tools that have been applied to address the problem of keeping reactants and products in a homogeneous phase.
Journal of Food Engineering, 2005
The group-contribution with association equation of state (GCA-EoS) is applied to represent high-... more 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 c 1 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.
Industrial & Engineering Chemistry Research, 2000
The use of near-critical CO 2 and propane for the removal of chemicalsspollutants, undesirable or... more The use of near-critical CO 2 and propane for the removal of chemicalsspollutants, undesirable or valuable productssfrom fatty oils is studied. The process conditions are discussed, on the basis of phase equilibrium predictions from a group contribution equation of state. The extension of the equation to cover systems with large differences in molecular size requires the use of revised parameters. With the new parameters, a good correlation of phase equilibrium data for all of the binaries involved in the process was achieved. Distribution coefficients of different chemicals between the oil and solvent phases were predicted, and optimum process conditions were explored. The extraction with propane requires the operation above the lower critical endpoint temperature of the binary fatty oil-propane system, to have liquid-liquid or liquidnear-critical fluid phase immiscibility. The process analysis indicates that there are optimum operating pressures that minimize solvent requirements and fatty oil losses in the extract.
Industrial & Engineering Chemistry Research, 2008
Transesterification reactions are common in the production of some important chemicals, such as b... more Transesterification reactions are common in the production of some important chemicals, such as biodiesel and mono-and diglycerides. Knowledge of the phase equilibrium conditions of the reactive mixture is essential to explore possible operating conditions for the reactor and the downstream separation process. In this work, liquidsliquid and vaporsliquidsliquid equilibrium data have been measured for the ternary system methyl oleatesmethanolsglycerol, at temperatures between 313 and 393 K. The group contribution with association equation of state (GCA-EOS) and the A-UNIFAC model were applied to represent the phase equilibria of this ternary system. Self-association in glycerol and methanol and cross-association with methyl esters were taken into account.
Fluid Phase Equilibria, 1992
... have been 03783812 92 05.00 1992 Elsevier Science Publishers BV All rights reserved 86 report... more ... have been 03783812 92 05.00 1992 Elsevier Science Publishers BV All rights reserved 86 reported (Martin and Collie, 1932; Papousek and ... Antoine parameters SD data range(K) ABC points Anisole 19 314427 7.110157 1446.845 73.987 0.65 Benzene 15 291354 6.940662 ...
Fluid Phase Equilibria, 2008
The transesterification of vegetable oils, esterification of fatty acids and glycerolisis reactio... more The transesterification of vegetable oils, esterification of fatty acids and glycerolisis reactions, with supercritical alcohols, are of interest in the production of specialty chemicals and biodiesel. The partial miscibility between the reactants and products of these processes have raised interest in the multiple phase behavior under reaction and separation conditions of mixtures of triglycerides and derivatives, fatty esters, alcohols and glycerin. In the present work, recent experimental studies under separation and reaction conditions are compared with modeling predictions using a group contribution with association equation of state.
Fluid Phase Equilibria, 1997
Phase equilibria of ternary ethane propane-sunflower oil mixtures were measured at 313, 333 and ... more Phase equilibria of ternary ethane propane-sunflower oil mixtures were measured at 313, 333 and 353 K, and at pressures of up to 120 bar. The region of partial liquid miscibility, at high hydrocarbon concentration, was particularly explored. The Soave-Redlich-Kwong equation of state was used to fit experimental vapor-liquid and liquid-liquid equilibria of alkane-vegetable oil mixtures. The application of a quadratic
… Congress of Chemical …, 2000
The Group Contribution Equation of State GC-EOS has been satisfactory applied to the modeling of ... more The Group Contribution Equation of State GC-EOS has been satisfactory applied to the modeling of high-pressure phase equilibria of supercritical gases (CO2, propane, ethane, dimethylether) with pure triglycerides and natural vegetable oils. The GC-EOS model size-...
Journal of Chemical & …, 1997
Vapor-liquid equilibria (VLE) for propylene + ethanol, propylene + methyl ethyl ketone (MEK), and... more Vapor-liquid equilibria (VLE) for propylene + ethanol, propylene + methyl ethyl ketone (MEK), and propylene + methyl tert-butyl ether (MTBE) were measured in the temperature range of (333 to 368) K and at pressures up to 45.5 bar. The systems show no azeotrope formation.
Industrial & Engineering Chemistry Research, 2002
Rigorous thermodynamic modeling, simulation, and optimization of the supercritical fractionation ... more Rigorous thermodynamic modeling, simulation, and optimization of the supercritical fractionation of EPA and DHA esters is presented. These valuable products are obtained from complex mixtures of fish oil fatty acid alkyl esters by high-pressure fractionation with supercritical carbon dioxide. A group contribution equation of state (GC-EOS) that provides reliable phase equilibrium and solubility predictions is used to support the process
Computers & Chemical Engineering, 1995
An extended UNIFAC group contribution model for the prediction of activity coefficients in associ... more An extended UNIFAC group contribution model for the prediction of activity coefficients in associating mixtures was presented recently (Mengarelli et al., 1999). In the present work the model is applied to solutions containing alcohols, water carboxylic acids and inert components. The residual UNIFAC local composition term is re-parameterized in order to take into account only dispersive forces between associating and inert functional groups. Good representation of vapor-liquid and liquid-liquid equilibrium, as well as infinite dilution activity coefficients is achieved by using a single set of group interaction parameters.
A modifed UNIFAC group contribution model for the prediction of activity coefficients in associat... more A modifed UNIFAC group contribution model for the prediction of activity coefficients in associating mixtures was proposed recently (Mengarelli et al., 1999). In the present work, the model is extended to carboxylic acids by defining a general associating group which ...
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Papers by Esteban Brignole