Resumo em Inglês:

Methylxanthines are alkaloids found in natural products such as tea, coffee and guaraná. These alkaloids are commonly used in cola drinks and pharmaceutical products due principally to their stimulant and diuretic effects on the human organism. In this work, experimental data on the supercritical CO2 extraction of caffeine, theophylline and theobromine from herbal maté tea, a beverage traditionally consumed by the gauchos of southern Brazil, the Argentine, Paraguay and Uruguay, were obtained using high pressure extraction equipment that allows adequate control of temperature and pressure. The continuous extraction/fractionation of maté tea leaves, Ilex paraguariensis in natura using carbon dioxide was carried out at 313.2 and 343.2 K and pressures of 13.8 and 25.5 MPa. Extraction/fractionation curves revealed the large influence of temperature and pressure on extraction yield. CO2 was also found to show a higher selectivity for caffeine than for theophylline and theobromine.

Resumo em Inglês:

Extraction with supercritical solvents has been used in different areas, such as petroleum desasphaltation, descaffeination of coffee and tea and in the separation of other types of natural products. The supercritical solvent most frequently utilized in the extraction of natural products is carbon dioxide (CO2) due to its several advantages over other solvents such as low cost, atoxicity and volatility. The design, evaluation and optimization of a supercritical extraction that is based on phase equilibrium require phase equilibrium data. This type of data is very scarce for natural compounds like sterols and vitamins. These natural compounds are produced synthetically, but nowadays interest in their extraction from natural sources is increasing. Therefore, the objective of this work is to study the thermodynamic modelling equilibrium of systems containing vitamins A, D, E and K, using the predictive LCVM model. The sensitivity of critical properties in the calculation of the phase behavior was also studied. This study proved that the choice of a group contribution method to calculate thermodynamic properties is very important for obtaining good results in the phase equilibrium calculations.

Resumo em Inglês:

Stevia leaves are an important source of natural sugar substitute. There are some restrictions on the use of stevia extract because of its distinctive aftertaste. Some authors attribute this to soluble material other than the stevia glycosides, even though it is well known that stevia glycosides have to some extent a bitter taste. Therefore, the purpose of this work was to develop a process to obtain stevia extract of a better quality. The proposed process includes two steps: i) Pretreatment of the leaves by SCFE; ii) Extraction of the stevia glycosides by SCFE using CO2 as solvent and water and/or ethanol as cosolvent. The mean total yield for SCFE pretreatment was 3.0%. The yields for SCFE with cosolvent of stevia glycosides were below 0.50%, except at 120 bar, 16°C, and 9.5% (molar) of water. Under this condition, total yield was 3.4%. The quality of the glycosidic fraction with respect to its capacity as sweetener was better for the SCFE extract as compared to extract obtained by the conventional process. The overall extraction curves were well described by the Lack extended model.

Resumo em Inglês:

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.

Resumo em Inglês:

The pupunha (Guilielma speciosa) is the fruit of a palm tree typical of the Brazilian Northern region, whose stem is used as a source of heart of palm. The fruit, which is about 65% pulp, is a source of oil and carotenes. In the present work, an analysis of the kinetics of supercritical extraction of oil from the pupunha pulp is presented. Carbon dioxide was used as solvent. The extractions were carried out at 25 MPa and 323 K and 30 MPa and 318 K. The chemical composition of the extracts in terms of fatty acids was determined by gas chromatography. The amount of oleic acid, a saturated fatty acid, in the CO2 extracts was larger than that in the extract obtained with hexane. The overall extraction curves were modeled using the single-parameter model proposed in the literature to describe the desorption of toluene from activated coal.

Resumo em Inglês:

Process simulation involves the evaluation of output variables by the specification of input variables and process parameters. However, in a real process, input data and parameters cannot be known without uncertainty. This fact may limit the utilization of simulation results to predict plant behavior. In order to achieve a more realistic analysis, the procedure of stochastic simulation can be conducted. This technique is based on a large set of simulation runs where input variables and parameters are randomly selected according to adequate probability density functions. The objective of this work is to illustrate the application of a stochastic simulation procedure to the process of fractionation of orange essential oil, using supercritical carbon dioxide in a multistage extraction column. Analysis of the proposed example demonstrates the importance of the stochastic simulation to develop more reliable designs and operating conditions for a supercritical fluid extraction process.

Resumo em Inglês:

Increasing restrictions on the use of artificial pigments in the food industry, imposed by the international market, have increased the importance of raw materials containing natural pigments. Of those natural substances with potential applications turmeric rhizomes (Curcuma longa L), are one of the most important natural sources of yellow coloring. Three different pigments (curcumin, desmetoxycurcumin, and bis-desmetoxycurcumin) constitute the curcuminoids. These pigments are largely used in the food industry as substitutes for synthetic dyes like tartrazin. Extraction of curcuminoids from tumeric rhizomes with supercritical CO2 can be applied as an alternative method to obtain curcuminoids, as natural pigments are in general unstable, and hence degrade when submitted to extraction with organic solvents at high temperatures. Extraction experiments were carried out in a supercritical extraction pilot plant at pressures between 25 and 30 MPa and a temperature of 318 K. The influence of drying pretreatment on extraction yield was evaluated by analyzing the mass transfer kinetics and the content of curcuminoids in the extracts during the course of extraction. The chemical identification of curcuminoids in both the extract and the residual solid was performed by spectrophotometry. Mass transfer within the solid matrix was described by a linear first-order desorption model, while that in the gas phase was described by a convective mass transfer model. Experimental results showed that the concentration profile for curcuminoids during the supercritical extraction process was higher when the turmeric rhizomes were submitted to a drying pretreatment at 343 K.

Resumo em Inglês:

A specially designed high-pressure cell was used simultaneously as extractor/autoclave and photometric cell in a Perkin Elmer Lambda 5 spectrophotometer. Based on this cell, a simple method was developed to determine the extractability of pigments by pure and by modified supercritical (sc) CO2. The method is demonstrated with curcumin from turmeric. With sc CO2 modified by 10% ethanol, the extraction yield for curcumin from two commercial finely ground dry turmeric samples was about 100%, measured by reference to the (complete) extraction of samples of the same charge with pure ethanol under standard conditions. Extractable curcumin content was from 1.8 to 2.5%, with three samples of turmeric of different origins.

Resumo em Inglês:

Supercritical CO2 extraction has shown great potential in separating vegetable oils as well as removing undesirable oil residuals from natural products. The influence of process parameters, such as pressure, temperature, mass flow and particle size, on the mass transfer kinetics of different natural products has been studied by many authors. However, few publications have focused on specific features of the raw material (moisture, mechanical pretreatment, bed compressibility, etc.), which could play an important role, particularly in the scale-up of extraction processes. A review of the influence of both process parameters and specific features of the material on oilseed extraction is given in Eggers (1996). Mechanical pretreatment has been commonly used in order to facilitate mass transfer from the material into the supercritical fluid. However, small particle sizes, especially when combined with high moisture contents, may lead to inefficient extraction results. This paper focuses on the problems that appear during scale-up in processes on a lab to pilot or industrial plant scale related to the pretreatment of material, the control of initial water content and vessel shape. Two applications were studied: deoiling of wheat gluten with supercritical carbon dioxide to produce a totally oil-free (< 0.1 % oil) powder (wheat gluten) and the extraction of oil from rose hip seeds. Different ways of pretreating the feed material were successfully tested in order to develop an industrial-scale gluten deoiling process. The influence of shape and size of the fixed bed on the extraction results was also studied. In the case of rose hip seeds, the present work discusses the influence of pretreatment of the seeds prior to the extraction process on extraction kinetics.

Resumo em Inglês:

Supercritical CO2 (SCO2) can be utilized to extract oils from a number of plant materials as a nontoxic alternative to hexane, and there is industrial interest in using SCO2 extraction to obtain high-quality oils for cosmetics and other high-value applications. A possible substrate is rosehip (Rosa aff. rubiginosa) seed. The scope of our work was to select SCO2 extraction conditions and to compare cold-pressed, hexane-extracted and SCO2-extracted rosehip oil. We used a fractional factorial experimental design with extraction temperature (T, 40-60 °C), extraction pressure (p, 300-500 bar) and dynamic extraction time (t, 90-270 min) as independent variables and yield and color as response variables. Samples of 100 g flaked rosehip seeds were extracted with 21 g CO2/min, following a static extraction (15 min adjustment) period. Resulting data were analyzed using response surface methodology. Extracted oil (4.7-7.1% in our experimental region) increased slightly with p and more pronouncedly with T and specially t. On the other hand, the photometric color index was independent of t but worsened (increased) as a result of an increase in either p or specially T. We extracted five batches of 250 g seeds with 21 g CO2/min at 40 °C and 300 bar for 270 min and compared the oil with samples obtained by solvent extraction (a batch of 2.5 kg of laminated seeds was treated with 10 L hexane and rotaevaporated until there was virtually no residual hexane) and cold pressing, by determining color, fatty acid composition, iodine index and saponification index. It was concluded that SCO2 allows an almost complete recovery of rosehip oil (6.5% yield), which is of a better quality than the oil extracted with hexane. Yield was higher than it was when using a cold-pressing process (5.0% yield).

Resumo em Inglês:

This paper presents the utilization of a stochastic global optimization method for the problem of parameter estimation in thermodynamic models. The method is based on an adaptation of the simulated annealing method to continuous variables. The proposed approach is applied to a vapor-solid equilibrium with supercritical carbon dioxide as solvent. Numerical results indicate that the simulated annealing method calculated a set of parameter values associated with considerably smaller errors as compared with a traditional method of local optimization.

Resumo em Inglês:

In order to reduce energy consumption and to increase deasphalted oil yield, an old PETROBRAS deasphalting unit was converted for use in the process of supercritical solvent recovery. In-plant and pilot tests were performed to determine the ideal solvent-to-oil ratio. The optimum conditions for separation of the supercritical solvent from the solvent-plus-oil liquid mixture were determined by experimental tests in PVT cells. These tests also allowed measurement of the dew and bubble points, determination of the retrograde region, observation of supercritical fluid compressibility and as a result construction of a phase equilibrium diagram.

Resumo em Inglês:

Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.

Resumo em Inglês:

Supercritical CO2 extraction of essential oil from Thymus vulgaris leaves was studied using experimental data recently obtained in the Florys S.p.A. laboratory. Mass transfer coefficients in the supercritical and solid phases from extraction curves at 40°C and 20 MPa were evaluated using a mathematical model based on the local adsorption equilibrium of essential oil on lipid in leaves. The adsorption equilibrium constant was fitted to these experimental data, and internal and external mass transfer resistances were calculated, allowing identification of the mechanism controlling the extraction process.