This work provides a general insight on lipase-catalyzed synthesis of geranyl acetate through esterification of geraniol with acetic acid. Although this reaction is relatively well known, the replacement of organic solvents by supercritical fluids is fairly recent and the role of CO2 is still not completely understood. Therefore, reactions were performed with Lipozyme® RM IM and Novozym® 435 as biocatalysts, and hexane and CO2 as solvents. For similar reaction conditions, geraniol conversions obtained using hexane were much higher, rather than supercritical CO2 (scCO2, 82.9% versus 12.0% after 4 h). The results obtained indicated that CO2 might help the migration of water from the enzyme surface to reaction bulk and then to the vapor phase. Thus, by increasing the vapor phase extension, the geraniol conversion enhanced to 60.5% after 4 h. Such improvement represents one step forward to comprehend the influence of CO2, a safer and greener solvent as compared to hexane.

Abstract This work presents the processing of a high-acidity oil through sequential reactions of esterification using montmorillonite K10 and transesterification using zinc monoglycerolate. Since these solids had not been employed along with this approach beforehand, the objective of this work is to provide a general insight of the proposed process and demonstrate its technical feasibility. In this sense, the processing of a synthetic mixture containing soybean oil and lauric acid provided a reduction of the free fatty acid content from (40.8±0.1) % to (3.1±0.4) % after the esterification reaction and a fatty acid methyl ester yield of (95.4±0.2) % was obtained after the transesterification reaction. As compared to traditional homogeneous catalysts, the solid catalysts employed in this work require higher reaction times to achieve satisfactory ester yields but, on the other hand, they are less sensitive to the presence of both water and free fatty acids in the raw materials and can be easily recovered and reused. Therefore, the results accomplished may help the development of a technology for processing high-acidity fatty materials in order to obtain biodiesel, although its economic feasibility still needs a further assessment.

ABSTRACT Asphaltenes represent the heaviest fraction of crude oils, being recognized by their tendency to self-associate and precipitate. Asphaltene precipitation and subsequent deposition can cause problems in all stages of production. The objective of this paper is to model Brazilian crude oil and asphaltene systems using the PC-SAFT equation of state. Asphaltenes were extracted from crude oil through the addition of different n-alkanes. The PC-SAFT was capable of accurately predicting liquid density for toluene and asphaltenes and boiling point elevation for crude oil at different concentrations of toluene. Asphaltene precipitation from model oil allowed us to evaluate the influence of binary interaction parameters on modeling results. The influence of precipitant agent (n-hexane and n-heptane) on the asphaltene phase behavior was analyzed, showing that n-hexane was able to precipitate more asphaltenes than n-heptane, as expected. Furthermore, simulated results are in agreement with experimental observations: the average relative errors are 3.75 % and 10.25 % for the weight percentage of precipitated asphaltene using n-hexane and n-heptane as precipitant, respectively.

Abstract This work reports a new set of experimental data for the liquid-liquid equilibrium (LLE) of the system (soybean oil + ethyl acetate + anhydrous ethanol) and the kinetics of crude oil extraction from soybean flakes using anhydrous ethanol + ethyl acetate mixtures. Data for the LLE binodal were measured at 298.15, 313.15 and 333.15K by the cloud point method and tie-lines were obtained at 298.15 and 313.15 K. LLE data were successfully modeled using the NRTL model. Batch extractions were performed at 298.15, 313.15 and 328.15 K at a fixed (4:1) solvent to soybean flake mass ratio and two concentration of ethyl acetate (5% and 10%) in ethanol. Higher temperatures increased the solubility of the system and improved the extraction yields. In addition, higher ethyl acetate ratios in anhydrous ethanol led to an increase in the total amount of crude oil extracted when operating at 298.15 and 313.15 K. At 328.15 K, no improvement in extractions was verified when 5% and 10% of ethyl acetate were used in the ethanol. A mass transfer model based on Fick’s Law was applied to describe the extraction kinetics, presenting an average relative deviation of ± 5.11%, in terms of extraction yield.

A simple method of home made preparation and physical-chemical characterization of orange wine was investigated. Saccharomyces cerevisiae was used as inoculum for wine-making by fermentation. Chemical compositions related to the aroma components seems to be very similar between grape and orange wines.