PROCESS FOR EXTRACTING NATURAL PRODUCTS BY MEANS OF SUPERCRITICAL FLUIDS

Abstract: PROCEDURE TO EXTRACT NATURAL PRODUCTS by means of a high pressure process using liquid solvents in the presence of supercritical fluids at a proportion less than 50%, at a pressure of between 50 and 500 bar, at a temperature less than 80ºC, for a time between 0.25 and 20 hours.

Description: PURPOSE OF THE INVENTION This invention refers to a procedure to extract organic products from vegetable or animal matrices, or their extracts, by means of high-pressure extraction using conventional liquid solvents and in presence of small amounts of supercritical fluids. BACKGROUND OF THE INVENTION In the bibliography currently in circulation, the following inventions are significant: JP 02235997 (Preparation of alga aromas by extraction with supercritical or semi-critical carbon dioxide in the presence of water or alcohol), US 4675198 (Extraction of aromas from vegetable products using liquid or supercritical extractors), JP 62036178 (Extraction and separation of organic compound of grape skin), DE 2737794 (Decaffeinisation of coffee by extraction with a solvent), DE 2638383 (Elimination of caffeine from coffee). There are also a significant number of publications which are close to this procedure, although it should be borne in mind that these processed follow the strategy of using supercritical CO 2 in the presence of small amounts or organic and/or inorganic solvents. A process for the extraction of oils from oil-containing solid vegetable material by means of a mixture consisting of a supercritical gas and a subcritical entraining agent is disclosed in U.S. 5,210,240. There are a series of inconveniences with current methods, such as the need to use large equipment and a high level of energy to produce relatively small amounts. This is because solvents are used with small solubilities or solvents which are not saturated when leaving the extractor as a result of the slow kinetics of extraction involved, and therefore the consumption of solvent per unit of extracted active product mass, is very high. With current techniques, substances are being extracted from vegetable matrices with pure or modified supercritical CO 2 with a small proportion of organic solvent (ethanol, acetone, hexane, methanol, water, etc.), which is always in a proportion less than 50%. DESCRIPTION OF THE INVENTION The procedure involved in this invention includes macerating at pressures of between 50 and 500 bar, the initial material in a solvent such as water, hydrocarbon, alcohol, ketone, ether, carbon halide or a mixture of these, containing a supercritical fluid (SCF) in a proportion of less than 50% of the total so that the resulting extraction mixture is a mixture of phases. The high working pressure causes the penetration of SCF, as it reduces its viscosity and increases diffusivity. This increase in diffusivity and reduction in viscosity causes the mobility of SCF through the inside of the cells and allows substances to be extracted at a much higher speed and in greater quantities than the conventional extractions or in other existing extraction patents to date. Apart from atmosphere extraction which avoids oxidations, it is also carried out at such moderate temperatures, slightly higher than room temperature, which drastically reduces the risk of decomposition of heat-labile products. The extraction mechanism means that the product extracted by the SCF is solvated quickly with traditional solvent, setting a balance between solute-SCF-conventional solvent which allows extraction to be performed at all times with the same levels of effectiveness and performance as at the start of the process. There is a continuous transfer of matter from the cells to the conventional solvent, using an intermediate phase formed by the SCF. The innovation of the process over existing processes lies in the fact that proportions between SCF and conventional solvent are inverted, meaning that the resulting mixture is not an SCF but a mixture of phases. This process means that the main solvent is not a SCF but ethanol, water or other solvents, which are found in greater proportions. The SCF does not act as a solvent but as a transport vehicle between the vegetable matrix and the solvent. This procedure minimises extraction time, reduces the solvent/solute ratio and therefore reduces pumping costs, the consumption of solvent and costs for its later recuperation. As quick extraction kinetics are present, the volume of the extractor is reduced for a certain production, or the production increases for a determined volume of extraction. This type of extraction can be applied to the extraction of organic products such as essential oils, dyes, alkaloids, lipids, oils, waxes, proteins, fatty acids, aromas, spices, isoprenoids, steroids, carotenes, or active pharmaceutical principles present in, or originating from extracts provided by the technique, such as oleoresin or adsorbate, or present in or originating from biological matrices, such as orange skin, paprika, grape skin, coffee, tea, medicinal plants, seeds, carrot or fish viscera. The time required to perform this operation is generally between 0.5 and 5 hours. The extracted product which is dissolved in the solvent is collected after depressurisation. This technique can be combined with a separation phase which allows the extract to be recuperated or fractionated. This recuperation or fractionating can be carried out following any process offered by the technique. Below we detail, as an example, the results obtained by applying the invention procedure to different matrices. Example 1.- Extraction of oleoresin from paprika. 140 gr. of ground paprika, 320 gr. of ethanol and 60 gr. of CO2 are mixed for 30 minutes at 250 bar and 40°C. The extract is concentrated by vacuum evaporation. 42 gr. of oleoresin are obtained. Example 2.- Extraction of malvidin from grape skin. 100 gr. of grape skin, 280 gr. of ethanol and 150 gr. of CO 2 are mixed for 30 minutes at 150 bar and 80°C. The extract is concentrated by vacuum evaporation. 125 mg. of malvidine are obtained, approximately 70% of the total. This extract is of a very aromatic nature, which proves that the aromas present in the skin are also recuperated during extraction. Example 3.- Extraction of essential oil, carotenes and flavonoids of orange skin. 150 gr. of dehydrated orange skin, 250 gr. of ethanol and 20 gr. of CO2 are mixed for 30 minutes at 50 bar and 70°C. The extract is concentrated by vacuum evaporation. 9 gr. of oleoresin is obtained, composed of carotenes and flavonoids of the orange skin together with some pectins, free from degradation products, which are very aromatic and stable. Example 4.- Extract of oil from grape seeds. 77.6 gr. of finely ground grape seeds, 225 gr. of hexane and 60 gr. of CO 2 are mixed for one hour at 280 bar and 40°C. The extract is concentrated by means of vacuum evaporation. The dry extract totals 9.25% of the total weight of the seeds used, its composition being: 73% of linoleic acid, 16% in oleic acid, 8% in palmitic acid, 3% stearic acid and 0.3% linolenic acid. Example 5.- Extraction of orange albedo pectins. 100 gr. of dry and finely ground albedo, 350 gr. of acidified water with nitric acid up to pH 2 and 40 gr. of CO 2 are mixed for one hour at 280 bar and 80°C. The extract is concentrated by vacuum evaporation. Ethanol is added to the residue after water evaporation, with which 1.3 gr. of pectins are precipitated. Example 6. Extraction of oil from fishmeal . 200 gr. of fishmeal, 170 gr. of hexane and 60 gr. of CO 2 are mixed for one hour at 250 bar and 50°C. The extract is concentrated by vacuum evaporation. 13 gr. of oil are obtained. The composition of this oil is: 6% myristic acid, 19% palmitic acid, 7% palmitoleic acid, 19% oleic acid, 8% EPA, 8% DHA, 12% non-unidentified fatty acid (owing to lack of reference), another 12% of another non-identified fatty acid (owing to lack of reference), and the remaining 9% composed of myristoleic, pentadecanoic, stearic, heptadecanoic, linoleic and linolenic acids. 1,209 ppm of vitamin A, 122 ppm of vitamin E and small amounts of other vitamins were also found. Example 7.- Recuperation of oil adsorbed by decolorant earth used in refining this oil. 200 gr. of material with a composition of 76 gr. of adsorption earth, 40 gr. of moisture and 84 gr. of adsorbed olive oil are mixed with 100 gr. of hexane and 40 gr. of CO 2 for 30 minutes at 280 bar and 40°C. The extract is concentrated by vacuum evaporation. 68 gr. of edible quality olive oil are obtained. Example 8.- Extraction of essential oil from rosemary . 100 gr. of dehydrated rosemary, 200 gr. of hexane and 60 gr. of CO 2 are mixed for 30 minutes at 150 bar and 40°C. The extract is concentrated by vacuum evaporation. 5.7 gr. of oil are obtained. Example 9.- Extraction of antioxidants from rosemary. 100 gr. of dehydrated rosemary, 200 gr. of water and 60 gr. of CO 2 are mixed for 30 minutes at 150 bar and 40°C. The extract is concentrated by vacuum evaporation. 5.5 gr. of watersoluble extract are obtained. Example 10.- Extraction of essential oils and oleoresin from Curcuma long a rhizome. 125 gr. of Curcuma longa rhizome, 450 gr. of azeotropic ethanol and 100 gr. of CO 2 are mixed for 30 minutes at 250 bar and 45°C. The extract is concentrated by vacuum evaporation. 6.4 gr. of oleoresin are obtained, which contain 2.9 gr. of curcumin, equivalent to 46% of curcumin present in the initial rhizome.

Claims: Procedure for high pressure extraction of organic products from vegetable or animal matrices or extracts thereof characterised in that it comprises mixing an organic product with one or more liquid solvents and one or more supercritical fluids so that the resulting extraction mixture is a mixture of phases and the proportion of the supercritical fluid is of less than 50% by weight based on the total weight of the solvent and the supercritical fluid. Procedure according to claim 1, characterised in that the pressure during the extraction process remains within 50 and 500 bar. Procedure according to claim 1, characterised in that the solvent or solvents are selected from the group consisting of water, hydrocarbon, alcohol, ketone, ether, carbon halide, hexane or mixtures thereof. Procedure according to claim 1, characterised in that the supercritical fluid is selected form the group consisting of CO 2 , propane, ethane. Procedure according to claim 3, characterised in that the supercritical fluid is selected form the group consisting of CO 2 , propane, ethane. Procedure according to claim 5, characterised in that the extraction time is generally between 0,5 and 5 hours.

Inventors: BLASCO PIQUER MIGUEL, FAUS FORTEA GERARDO, MARTINEZ FUENTES JUAN GABRIEL, MIRA FERRI BAUTISTA ENRIQUE, SUBIRATS HUERTA SEBASTIAN, BLASCO PIQUER, MIGUEL, FAUS FORTEA, GERARDO, MARTINEZ FUENTES, JUAN GABRIEL, MIRA FERRI, BAUTISTA ENRIQUE, SUBIRATS HUERTA, SEBASTIAN, SUBIRATS HUERTA, Sebastián
Applicants: INVEST DE LA IND AGROALIMENTAR, ASOCIACION DE INVESTIGACION DE LA INDUSTRIA AGROALIMENTARIA
Application year: 1997
Main classification: A61K35
IPC codes: A61K35, B01D11, A61K36