ABSTRACT Duguetia furfuracea (Annonaceae) is a shrub found in the Brazilian Cerrado that is used in popular medicine as an antirheumatic, for wound healing, treatment of kidney pain and against pediculosis. The aim of this study was to analyze the extraction of leaves of Duguetia furfuracea, using supercritical CO2, ethanol and hexane as solvents. For the supercritical extraction, an experimental planning 23 with triplicates of the central point was used to evaluate the effects of temperature (313-333 K), pressure (15-23 MPa) and volumetric flow rate (3-6 mL min-1) on the extraction yield, total phenolic content and antioxidant activity compared with extracts obtained by Soxhlet extraction. The effects of the variables on the extraction yield were positive and the pressure had greater influence. However, the highest performances, total phenolic content and antioxidant activities were obtained by the Soxhlet method. The mathematical model based on the Brunauer-Emmett-Teller theory of adsorption correlated satisfactorily the experimental values of the supercritical extraction.

ABSTRACT This study evaluated the potential of macauba pulp oil (MPO) as a feedstock for continuous ester production using ethanol under pressurized conditions. Experiments were performed in order to obtain data for the effect of process variables on ethyl ester (FAEE) and free fatty acid (FFA) conversion in a catalyst-free process. From the results, it appears that the MPO to ethanol mass ratio and the pressure were the variables with more favorable effect on the evaluated response variables. The addition of n-hexane caused an increase in the production of esters; however, this had a negative effect on FFA conversion. The addition of water was unfavorable for oil processing with high acidity. In this process, esterification and transesterification occur simultaneously, and the high FFA content in MPO provides high yields (85 wt% of esters; 93% FFA conversion) at low temperature, since the esterification reaction rate is higher than the transesterification. The decomposition of fatty acids was evaluated and levels <5% were observed under the evaluated experimental conditions.

Abstract The Supercritical Antisolvent (SAS) technique allows for the precipitation of drugs and biopolymers in nanometer size in a wide range of industrial applications, while guaranteeing the physical and chemical integrity of such materials. However, a suitable combination of operating parameters is needed for each type of solute. The knowledge of fluid dynamics behavior plays a key role in the search for such parameter combinations. This work presents a numerical study concerning the impact of operating temperature and pressure upon the physical properties and mixture dynamics within the SAS process, because in supercritical conditions the radius of the droplets formed exhibits great sensitivity to these variables. For the conditions analyzed, to account for the heat of mixture in the energy balance, subtle variations in the temperature fields were observed, with almost negligible pressure drop. From analyses of the intensity of segregation, there is an enhancement of the mixture on the molecular scale when the system is operated at higher pressure. This corroborates experimental observations from the literature, related to smaller diameters of particles under higher pressures. Hence, the model resulted in a versatile tool for selecting conditions that may promote a better control over the performance of the SAS process.

In the present study, the transesterification of Jatropha oil in a continuous catalyst-free process using supercritical ethanol was investigated. Experiments were performed in a packed-bed tubular reactor by studying the effect on the reaction of temperature, pressure, water and cosolvent (n-hexane) concentrations, keeping the oil:ethanol mass ratio fixed at 1:1 for different residence times. The results demonstrated that temperature and pressure had a positive effect on fatty acid ethyl ester (FAEE) production and it was observed that the free fatty acids present in vegetable oil promote faster reaction kinetics due to simultaneous esterification and transesterification reactions. The addition of water and a cosolvent increased the FAEE yields at 573 K and 20 MPa. Within the experimental ranges investigated, water and the cosolvent decreased the decomposition of fatty acids. Appreciable reaction yields (~90 wt%) were achieved at 573 K, 20 MPa, with an oil:ethanol mass ratio of 1:1 and 10 wt% water.

Growing environmental concerns, along with the search for renewable energies that emit less CO2, put biodiesel in a favorable position. Biodiesel is commonly produced by the transesterification reaction between vegetable oils and methanol or ethanol, in the presence of a catalyst. With government incentives for biodiesel production in Brazil, there was an exaggerated increase in their production and hence the concern about the disposal of surplus glycerol. Therefore research is being developed with respect to the use of the surplus of glycerol. In this context, emerged as the alternative use of fuel additives, from glycerin to contribute to the development of new applications for innovative and environmentally-friendly processes. The bibliographic review presented here starts with describing the different glycerol production processes, characterization and analysis methods. Next, Glycerol-based processing methods are described, evaluating the main reaction parameters that interfere in process optimization

Miniemulsification and emulsion/solvent evaporation techniques were combined to produce poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanoparticles. Those nanoparticles were prepared with different PHBV molar masses and PHBV concentrations to verify their effect on the final particle size. Nanoparticles with an average diameter of 133 nm were obtained when a low molar mass (Mw = 44,350 g/mol) polymer was used. On the other hand, when high molar mass PHBV (Mw = 369,900 g/mol) was used under the same operational conditions, nanoparticles with a 300 nm average diameter and a broader particle size distribution were formed. Results also showed that increasing the PHBV concentration led to an increase of the particle size and, when the polymer/costabilizer (PHBV/hexadecane) weight ratio was close to 1, nanocapsules (hexadecane core surrounded by a PHBV shell) were formed.

This work is focused on the determination of liquid-liquid equilibrium data for systems containing methyl and ethyl fatty acid esters, water, glycerol and ethanol at temperatures of 303.15 K and 318.15 K using a near-infrared spectroscopy technique (NIR). The NIR method used in this investigation provided quite satisfactory results when compared to conventional analytical techniques and hence can be used as an advantageous tool to quantify the compounds involved in the liquid-liquid equilibrium systems: i) without previous preparation of the samples; ii) with less waste generation; iii) at low cost; and iv) via a non-destructive technique, as sample analyses are made directly, showing good reproducibility and reliability of the data. The NIR method was effective in the use of different temperatures for calibration and validation of the systems under study. Besides, it is shown that extrapolation with the technique may be possible, making LLE predictions feasible for other conditions not used in the calibration procedure.

Minimization of Gibbs free energy using activity coefficient models and nonlinear equation solution techniques is commonly applied to phase stability problems. However, when conventional techniques, such as the Newton-Raphson method, are employed, serious convergence problems may arise. Due to the existence of multiple solutions, several problems can be found in modeling liquid-liquid equilibrium of multicomponent systems, which are highly dependent on the initial guess. In this work phase stability analysis of liquid-liquid equilibrium is investigated using the NRTL model. For this purpose, two distinct stochastic numerical algorithms are employed to minimize the tangent plane distance of Gibbs free energy: a subdivision algorithm that can find all roots of nonlinear equations for liquid-liquid stability analysis and the Simulated Annealing method. Results obtained in this work for the two stochastic algorithms are compared with those of the Interval Newton method from the literature. Several different binary and multicomponent systems from the literature were successfully investigated.

Phase equilibrium calculations at high pressures have been a continuous challenge for scientists and engineers. Traditionally, this task has been performed by solving a system of nonlinear algebraic equations originating from isofugacity equations. The reliability and accuracy of the solutions are strongly dependent on the initial guess, especially due to the fact that the phase equilibrium problems frequently have multiple roots. This work is focused on the application of a subdivision algorithm for thermodynamic calculations at high pressures. The subdivision algorithm consists in the application of successive subdivisions at a given initial interval (rectangle) of variables and a systematic test to verify the existence of roots in each subinterval. If the interval checked passes in the test, then it is retained; otherwise it is discharged. The algorithm was applied for vapor-liquid, solid-fluid and solid-vapor-liquid equilibrium as well as for phase stability calculations for binary and multicomponent systems. The results show that the proposed algorithm was capable of finding all roots of all high-pressure thermodynamic problems investigated, independent of the initial guess used.

Rapid expansion of supercritical solution (RESS) is a promising technique for microparticle production. The literature points out that the RESS technique can be applied to process a wide range of materials including ceramics, polymers, biopolymers, pharmaceutics, and organic compounds. In order to achieve an adequate understanding of the RESS process, it is necessary to conduct more comprehensive studies involving the hydrodynamic modeling of the fluid flow through the capillary, the phase behavior of a expanding mixture, and also with regard to the microparticle formation mechanism. In this context, this work is focused on the analysis of process hydrodynamic modeling and on phase equilibrium modeling (thermodynamic modeling of supersaturation), with a phase stability test coupled. The Gibbs tangent plane distance for the phase stability test was minimized using the simulated annealing algorithm. The results showed that the thermodynamic variables exert a remarkable effect simulated variables (temperature, velocity, density and degree of supersaturation) for the profile.

The tangent plane criterion has become important for a correct solution evaluation phase and chemical of equilibrium problem. This method, applicable to single and multiphase systems, is mainly used for a single equation of state modeling all phases involved. The present work is mainly concerned with the application of interval analysis methods for global energy minimization in high-pressure phase stability problems. Two approaches are applied: (i) the Gibbs free energy global minimization under conditions of constant temperature and pressure and (ii) the Helmholtz free energy density global minimization under conditions of constant temperature and volume. Five case studies, one ternary and four binary systems, are analyzed in connection with the Peng-Robinson equation of state (PREOS) model. Five more case studies, for the CO2 + trans-2-hexen-1-ol system at high pressures, are used to compare different methods of phase equilibrium calculation with the approach using interval analysis. Finally, a complex system, clove oil + CO2, is analyzed. The results indicate that the interval analysis method is robust and reliable for all the problems studied.

The compound R-(+)limonene is available and cheap than its oxidized products. Consequently, the selective oxidation of R(+)limonene has attracted attention as a promising process for the production of compounds with a higher market value, such as cis/trans-1,2-limoneneoxide, cis/trans-carveol and/or carvone. One of the these processes, described in the recent literature, is submission of R-(+)limonene to an oxidation reaction catalyzed by neutral or cationic Metal(Salen) complexes, in the presence of effective terminal oxidants such as NaOCl or PhIO. These reactions are commonly carried out in organic solvents (dichromethane, ethyl acetate, acetonitrile or acetone). Thus, the main objective of the present work was to study the effect of several factors (type of oxidant, catalyst, solvent and time) on reaction selectivity for the high-priced compounds referred to above. For this purposes, experimental statistical multivariate analysis was used in conjunction with a complete experimental design. From the results it was observed that for the three targeted products (1,2-limoneneoxide, carveol or carvone) some factors, including the nature of the terminal oxidant and the catalyst, were significant for product selectivity (with a confidence level of 95%). Therefore, this statistical analysis proved to be suitable for choosing of the best reaction conditions for a specific desired product.

The adsorption of two metal ions, Cr(III) and Cu(II), in single-component and binary systems by Sargassum sp., a brown alga, was studied. Equilibrium batch sorption studies were carried out at 30ºC and pH 3.5. Kinetic tests were done for a binary mixture (chromium + copper) for a contact time of 72 hours to guarantee that equilibrium was reached. The monocomponent equilibrium data obtained were analyzed using the Langmuir and Freundlich isotherms. The binary equilibrium data obtained were described using four Langmuir-type and Freundlich isotherms. The F-test showed a statistically significant fit for all binary isotherm models. The parameters for isotherms of the Langmuir-type were used to determine the affinity of one metal for the biosorbent in the presence of another metal. The chromium ion showed a greater affinity for Sargassum sp. than the copper ion.

One of the most important byproducts of the orange juice industry is the oil phase. This is a mixture of terpenes, alcohols, and aldehydes, dissolved in approximately 96% limonene. To satisfactorily use oil phase as an ingredient in the food and cosmetics industries separation of the limonene is required. One possibility is to use a fixed bed of silica gel to remove the light or aroma compounds from the limonene. The aroma substances are then extracted from the bed of silica gel using supercritical carbon dioxide. This work deals with the modeling of the desorption step of the process using mass balance equations coupled with the Langmuir equilibrium isotherm. Data taken from the literature for the overall extraction curves were used together with empirical correlations to calculate the concentration profile of solute in the supercritical phase at the bed outlet. The system of equations was solved by the finite volume technique. The overall extraction curves calculated were in good agreement with the experimental ones.