ABSTRACT The activity coefficient at infinite dilution (&IN1) and distribution ratios at infinite dilution (&IN2) were determined for alkanols (methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, and 2-methyl-2-propanol) in the ionic liquid (IL) 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][CH3SO4]) by HS-SPME (Headspace - Solid Phase Micro Extraction) at four temperatures (298.15, 313.15, 333.15, and 353.15K) using headspace - solid phase microextraction (SPME-HS). The results showed significant agreement with literature data. In addition, partial molar excess enthalpies at infinite dilution (&IN3), excess Gibbs energies (&IN4), and excess entropies (&IN5) were calculated from the (&IN6) values.

During the process of supercritical CO2 extraction it is necessary to use high pressures in the procedure. The explosion of a pressure vessel can be harmful to people and cause serious damage to the environment. The aim of this study is to investigate the probability of death and injury in a laboratory unit for supercritical fluid extraction in the case of an explosion of the extractor vessel. The procedure is explained via a case study involving fatty acid extraction from vegetable oils with carbon dioxide above its supercritical conditions and under optimum operating conditions. According to the results, more importance should be given to the use of a protective headset because the probability of eardrum injury is superior to the probability of death from lung injury.

The knowledge of the phase equilibrium is one of the most important factors to study the design of separation processes controlled by the equilibrium. Fatty acids are present in high concentration as by-products in vegetable oils but the equilibrium data involving these components is scarce. The objective of this work is the experimental determination of the liquid-vapor equilibrium of five binary different systems formed by carbon dioxide and palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2) and linolenic acid (C18:3). The equilibrium experimental data was collected at 40, 60 and 80ºC at 60, 90 and 120 bar, at the extract and raffinate phases, using an experimental apparatus containing an extractor, a gas cylinder and pressure and temperature controllers. The data was modeled using the cubic equation of state of Peng-Robinson with the mixing rule of van der Waals with binary interaction parameters. The model was adequate to treat the experimental data at each temperature and at all the temperatures together. The best model that includes the van der Waals mixing rule with two parameters has maximum deviation of 17%. The distribution coefficients were also analyzed and it was concluded that the fractionation of the fatty acids is possible using supercritical carbon dioxide.

Modified clays were used to remove ethyl acetate from aqueous solutions. These clays were regenerated using supercritical CO2. Structural changes in the montmorillonite clay after treatment with quaternary amines were studied. The surface properties of the modified clay changed from highly hydrophilic to highly organophilic. The clay was regenerated by percolation of a stream of CO2 through the porous montmorillonite matrix. Different pressures and temperatures were employed, resulting in different fluid conditions (gas, liquid, and supercritical). The experimental data was fitted with a simplified model. The best desorption result was found under supercritical conditions. A crossover effect was observed. The capacity of the modified clay as a pollutant attenuator remained almost unchanged after a regeneration cycle.

The main objective of this work is to study the regeneration capacity of modified clays using supercritical fluid. These modified clays are used as organic compound adsorvents. The experimental step was done using a packed column with the clay contaminated by toluene. The results obtained showed the influence of the density of the supercritical CO2 and of the organic modifier in the desorption process. These data were modeled with first- and second-order models. Better results were obtained using the second-order model. This study makes possible the scale-up of the desorption process for regeneration of solid matrices using supercritical fluids.