WO2003103645A1

WO2003103645A1 - Fractionated extraction of natural source carotenoids with a high lycopene content, using supercritical fluids

Info

Publication number: WO2003103645A1
Application number: PCT/ES2003/000262
Authority: WO
Inventors: María Salud GÓMEZ PRIETO; María Luisa RUIZ DEL CASTILLO; José Guillermo SANTA-MARÍA BLANCO; Gracia Patricia Blanch Manzano; Marta Herraiz Carasa
Original assignee: Consejo Superior De Investigaciones Científicas
Priority date: 2002-06-06
Filing date: 2003-05-30
Publication date: 2003-12-18
Also published as: AU2003232854A1; ES2197014B1; ES2197014A1

Abstract

The invention relates to a method of obtaining all-trans lycopene crystals smaller than 10 ?m and with a purity greater than 85 %. The inventive method can be used in the food, cosmetic and pharmaceutical industries as well as in the production of nutraceuticals and functional foods. Said environmentally-friendly method involves the use of supercritical fluids for the extraction and fractionation of tomato carotenoids.

Description

FRACTIONAL EXTRACTION OF CAROTENOIDS FROM NATURAL SOURCES WITH HIGH CONTENT IN LYCOPENE BY SUPERCRITICAL FLUIDS

SECTOR OF THE TECHNIQUE

The invention is related to the production of carotenoids from natural sources, mainly lycopene with high purity, by means of supercritical fluids, useful for the pharmaceutical, cosmetic and food industries. It is also related to the use of by-products and surpluses from the Agrifood Industry related to tomatoes.

STATE OF THE ART

Carotenoids have been widely studied both as natural dyes and for their antioxidant nature and their beneficial effects for human health. Lycopene is present in humans in serum and tissues, associated with cell membranes and forming aggregates in adipose tissues. It acts as an antioxidant, preventing diseases caused by free radicals such as cardiovascular, tumor pathologies and other disorders related to aging and / or degenerative processes. In addition, it seems to reduce chemically induced neoplasms. The accumulated evidence on their biological activity justifies that lycopene is considered a micro nutrient and recommended daily intake. All this has been the cause of the growing interest in the lycopene of consumers and industry, leading to an increase in its use in cosmetic preparations, pharmaceutical formulas and the manufacture of functional foods or food preparations used as a complement to the diet. The patents FR2770974, GB2274235, WO9948386 and WO0207768 describe the use of lycopene in dietetic products. In US6261598 and WO0126486 it is used mixed with other antioxidants and in WO0137781 it is part of a stable aqueous dispersion for application in foods. The patents FR2799368 and 2811569, JP2000229827, O0066078 and 9747278, describe the participation of lycopene in cosmetic products with protective effects against UN rays. In the pharmaceutical industry the patents US2002001633 and 6350776, WO0126668 describe lycopene preparations with preventive effects against different types of cancer. It also forms part of anti-hypercholesterolemic products (EP0759294, US6262109 and WO9938518), anti-free radicals (WO0007581 and US2002012714), diuretics (JP10158182) and prevention of liver diseases (WO0078325).

Lycopene is found in appreciable amounts in fruits and vegetables, mainly in tomato (30 to 100 ppm) and watermelon. However, in natural products its concentration is small and it is accompanied by other compounds, so it is necessary to extract and purify it so that it can be used in the food, cosmetic and pharmaceutical industries. It can also be obtained by chemical synthesis (US6040475; DE10009459; EP1072589). However, synthetic additives in the food industry are currently not well considered, being rejected by consumers, a fact that is spreading to the cosmetic and pharmaceutical industry. On the other hand, extraction from tomato and its derivatives affects the use of by-products and agrifood surpluses, which means benefits for both the producing sectors and the environment.

The large scale production of lycopene is based on its extraction, isolation and purification from natural sources, being essential to obtain it in crystalline form with size less than 10 μm. Most processes use organic solvents, purification and subsequent recrystallization of lycopene being generally necessary (WO9516363, CN1298904, RU2039775). The disadvantage of these methods is that the crystals usually retain residues of the solvent and require additional washes with more solvents, finally they must be dried generally at elevated temperatures that favor the isomerization of lycopene. This isomerization is not desirable since it is known that the cis-lycopene isomers are more unstable than the all-trans, natural isomer of lycopene. In addition, the washing steps for purifying the lycopene crystals cause appreciable amounts of wash water which is an environmental problem. To avoid the use of toxic solvents, processes have been described based on the direct obtaining of lycopene crystals by saponification (US5858700) in the presence or absence of calcium salts that act as anti-solvent (US 5245095), or extraction with ethanol at high temperature (US5871574, EP 1103579). These processes also generate appreciable amounts of wastewater and require high temperatures and high reaction times. On the other hand, all these processes are little or not selective so to obtain relatively pure lycopene (> 50%) it is necessary to purify the extract by means of procedures such as chromatographic (JP2138996, US3369974, CN1316468), crystallization (US4439629) or precipitation (WO9613178).

The technology of supercritical fluids, using a gas as a solvent under supercritical conditions, provides a selective extraction, allows easy separation of solutes without residues of the solvent, prevents the accumulation of wastewater, the process is carried out at moderate temperatures, in absence of light and in reducing medium without the presence of air and the lycopene is obtained in powder form. This technique has been used in the extraction and purification of carotenoids from natural matrices (EP0719866, US5264212, JP 07304977, US5789647, JP63112659).

Patent WO9832449 uses supercritical carbon dioxide (CO ₂ -SC) mixed with organic solvents (50%) to increase the extraction yield. The patent

EP0818225 uses CO ₂ -SC to purify lycopene starting from the oleoresin of the tomato previously extracted with organic solvents. The patents WO0179355 and JP7147929 describe the extraction of lycopene with CO ₂ -SC in the presence of a vegetable oil.

In the present invention we use this technology, as solvent supercritical carbon dioxide (CO ₂ -SC), as a natural source tomato and similar species are used, starting from the whole fruit or parts of it, coming from the surplus and by-products of the industry agrifood. Patents JP7147929 and WO0179355 describe processes for obtaining lycopene from tomato using supercritical carbon dioxide. Both patents use whole tomato or some of its parts in the form of dry powder. The most notable difference between these two patents and the process described in the present invention is that in none of these patents is an activated extraction performed, lycopene is obtained together with the rest of carotenoids of the tomato. In addition, both patents start from tomato powder previously dispersed in a vegetable oil. Patent US4400398 uses a fractional extraction process with which the carotenoids of the pepper, mainly xanthophylls, are separated from the components of the aroma, but it does not fractionate the carotenoids from each other. In the case of lycopene, no procedure has been described that, by means of fractional extraction with supercritical fluids, manages to separate the lycopene from the rest of the carotenoids.

DESCRIPTION OF THE INVENTION BRIEF DESCRIPTION OF THE INVENTION The present invention provides a method for extracting carotenoids from natural sources with a high lycopene content such as tomato, watermelon and similar species, as well as from algae and biomass from the fermentation of genetically modified microorganisms. to produce high lycopene content. Prior to extraction the starting material is dried and ground to obtain a powder. This powder with a low moisture content is subjected to extraction with a fluid under supercritical conditions, preferably carbon dioxide under pressure greater than its critical pressure and at temperature above its critical temperature. Simultaneously, as the extract is obtained, it is divided into three fractions by a simple change in pressure and / or temperature. The first fraction is made up of virtually pure trans-lycopene. The second fraction is constituted by a mixture of carotenoids in which the cis isomers of lycopene are present, with β-carotene, phytoene and phytofluene predominating. The third fraction is constituted by the aroma components. The two carotenoid fractions are obtained directly in the form of small crystals in suitable containers called separating cells. Once the process is finished, the crystals are recovered from the aforementioned separating cells. The fraction with the components of the aroma, whenever it is of interest, can be collected in a cold trap or retained in an adsorbent. Detailed description of the invention

The present invention relates to the extraction and fractionation of carotenoids contained in a natural source, preferably with a high lycopene content such as tomato.

According to the invention, it can be made from whole tomato, or some of its parts such as skin and pulp, or their mixtures, from surplus and by-products of the agri-food industry.

The present invention aims to obtain all-trans lycopene crystals with a size of less than 10 μm and a purity greater than 85% that can be used in the food, cosmetic and pharmaceutical industries, as well as in the manufacture of functional or nutraceutical foods, by means of a procedure that respects the environment. To this end, the technology of supercritical fluids has been used, avoiding the use of organic solvents, as well as the need for subsequent stages of crystallization and / or purification, which generate significant quantities of wastewater. The process described here consists of a single stage in which the extraction and fractionation of the carotenoids is carried out, originating a fraction formed practically by all-trans lycopene (more stable than the cis-lycopene isomers) and another fraction constituted by the rest of the carotenoids, both fractions being free from the aroma components. These two carotenoid fractions are useful for the food, cosmetic and pharmaceutical industries, as well as for the manufacture of functional foods or nutraceuticals. One of the fractions consists of all-trans-lycopene with a purity greater than 85%, preferably greater than 90%, and the other fraction is constituted by a mixture of carotenes, with β-carotene, phytoene or phyto-fluene predominating, depending on the source natural from which it is split. These two fractions are free of aroma components which are collected in a third fraction by a cold trap or by using an adsorbent.

Before being subjected to the extraction according to the method described in the present invention, the tomatoes or their parts have to be turned into powder to guarantee the breaking of the cell walls in order to facilitate the extraction of pigments. For this, one of the traditional procedures in which mechanical crushing, cooking, freeze-thawing, enzyme treatment, alcohol precipitation, centrifugation, homogenization and drying processes such as oven drying can be applied. , atomized and lyophilized. According to the present invention it is preferable to avoid thermal treatments and the addition of organic solvents, therefore, when part of whole tomato is preferable to use the mechanical crushing of previously chopped tomatoes and removed the locules, followed by a centrifugation and drying of the solid fraction obtained by lyophilization. When part of tomato pulp is homogenized and dried preferably by lyophilization. From the tomato skin it is simply dried, preferably by lyophilization. When starting from mixtures of pulp and tomato skin, the mixture is crushed and homogenized obtaining a porridge that is subsequently lyophilized. Then the lyophilized material is finely ground and homogenized; the moisture content of the powder obtained is less than 10% by weight. According to the present invention, when starting from other natural sources such as watermelon, algae or biomass from the fermentation of microorganisms, proceeds in the same way, also reaching a product in the form of dry powder.

To describe in detail the extraction and fractionation process, the diagram of Figure 1 will be used. According to the invention described herein, the extraction and fractionation process is carried out in a single stage beginning with the introduction of the natural source with high content of lycopene in the form of a dry powder in the extraction cell 7 (Fig. 1); then the compressed gas from the container 1 (Fig. 1), preferably carbon dioxide (CO ₂ ), is passed through the pipe 2 (Fig. 1) to the compressor 3 (Fig. 1) which compresses the carbon dioxide up to the extraction pressure between 25 and 40 MPa (pressure regulated by the valve 9 Fig. 1), preferably between 30 and 35 MPa. The carbon dioxide (CO ₂ ) at high pressure is introduced into the heat exchanger 5 (Fig. 1) through the pipe 4 (Fig. 1) in order to heat the compressed gas to the extraction temperature between 35 and 70 degrees centigrade, preferably between 40 and 65 degrees centigrade, putting the compressed gas, in supercritical conditions. Then carbon dioxide under supercritical conditions [also called supercritical carbon dioxide (CO ₂ -SC)] is introduced into the extraction cell 7 (Fig. 1) through the pipe 6 (Fig. 1) so that the fluid The supercritical material is brought into contact with the previously broken cells of the material in powder form found in the extraction cell 7 (Fig. 1) and extracts the lipid components present in said material. The supercritical fluid, preferably supercritical carbon dioxide, loaded with the extracted compounds leaves the extraction cell through line 8 (Fig. 1) and reaches valve 9 (Fig. 1) [which regulates the pressure in the extraction cell 7 Fig. 1]. When the supercritical fluid loaded with the extracted lipid compounds passes through the valve 9 (Fig. 1) it is introduced through the pipe 10 (Fig. 1) into the first separator cell 11 (Fig. 1). According to the present invention, in this first separator cell 11 (Fig. 1) the pressure of the supercritical fluid charged with the extracted lipid components is decreased to a value in the range of 10 to 20 MPa [pressure regulated by the valve 13 (Fig. 1)], preferably between 12 and 18 MPa, optionally, together with the pressure drop, the temperature can be varied from 5 to 10 degrees centigrade, increasing or decreasing it, depending on the initial composition of carotenoids in the material of Starting, this variation of the pressure and temperature supposes a decrease of the density of the supercritical carbon dioxide propitiating the precipitation of part of the lipid compounds contained in the supercritical fluid coming from the extraction cell, originating two fractions: a solid red color strongly intense, formed by all-trans-lycopene crystals in a percentage higher than 85%, preferably above or 90% and another fraction formed by the supercritical fluid loaded with the rest of the pigments, other more soluble lipids and aroma components. Occasionally, depending on the type of starting material, lycopene crystals of intense red color with a particle size of less than 10 μm are obtained dispersed in a colorless liquid with an oily appearance. The fraction formed by the supercritical fluid charged with the rest of the extracted components, not precipitated in the first extraction cell 11 (Fig. 1), is conducted through the pipe 12 (Fig. 1), the valve 13 (Fig. 1), which regulates the pressure in the separator cell 11 (Fig. 1) and the conduit 14 (Fig. 1) to the second separator cell 15 (Fig. 1) in which the pressure is decreased to a value comprised between 1.5 and 10 MPa, preferably subcritical, between 4 and 6 MPa and optionally, at the same time that the pressure is lowered, the temperature can be varied by increasing or decreasing it, depending on the value of the pressure. At high pressures the temperature could be slightly increased, preferably from 2 to 6 degrees centigrade; at low pressures do not vary the temperature, or in any case reduce it slightly, preferably to values close to the ambient temperature. The variations of pressure and temperature cause the separation or precipitation of the pigments present in the supercritical fluid, together with other lipid components of low volatility. Two fractions originate a red-orange oily-looking liquid that is deposited at the bottom of the separating cell 15 (Fig. 1) and another fraction formed by the fluid, gas under subcritical conditions that carries in suspension the most volatile compounds . The oily-looking fraction deposited in the separator cell 15 (Fig. 1) has a composition that depends on the natural source of the starting material. In the case of tomatoes, this oily fraction deposited in the separating cell 15 (Fig. 1) of red-orange color, is formed by carotenoids, sterols and free fatty acids, with β-carotene and phytoene or phytofluene predominating. cis isomers of lycopene and in lower concentration compounds such as lutein, tocopherols and andrin which acts as an antidepressant. The gas with the most volatile compounds in suspension leaves the separating cell 15 (Fig. 1) and through the conduit 16 (Fig. 1) passes through the valve 17 (Fig. 1) which controls the pressure in said separating cell 15 (Fig. 1). From valve 17 (Fig. 1) the gas is in normal conditions and the solutes in suspension can be recovered with a cold trap 19 (Fig. 1) or with an adsorbent of those traditionally used.

The time of the process depends on the starting material and its initial content in carotenoids. According to the invention described herein the extraction and fractionation time is comprised in the range of 1 hour to 24 hours, preferably between 3 and 9 hours and more preferably between 4 and 6 hours.

The yields of the extraction (percentage of extracted lycopene) are between 50% and 100%, depending on the starting material. In cases where it is necessary to increase the extraction performance, a modifier or co-solvent to the supercritical fluid, preferably water, in an amount comprised in the range 0.1% and 10% by weight, preferably between 0.1% and 1%. The SI fraction consists of crystals of carotenoids dispersed in a liquid formed mainly by triglycerides. The proportion in which the carotenoids are found is greater than 80%, although it depends on the starting material, preferably greater than 90%. The all-trans-lycopene is practically the only carotenoid present in this fraction, above 95%, preferably above 99%. The S2 fraction is constituted by carotenoids and other lipid components dissolved or dispersed in an oil formed by triglycerides and free fatty acids. This oil accounts for less than 45% by weight of the S2 fraction. Carotenoids account for more than 60% of fat-soluble compounds, preferably above 75%, with β-carotene, phytoene, phytofluene and lycopene predominating. The rest of the fat-soluble fraction is composed mainly of tocopherols, sterols and amirin, with α-tocopherol being the majority. It is noteworthy that amirin is an antidepressant present in this S2 fraction in proportions between 0.1% and 5%, depending on the starting material, the tomato variety, the degree of maturity, etc.

DESCRIPTION OF THE FIGURES

Figure 1. Represents the scheme of the equipment used. This equipment consists mainly of the following parts: a container (1) in which the compressed gas is located; of a compressor (3) that compresses the gas to a pressure greater than its critical pressure; of a heat exchanger (5) that heats the gas to a temperature above its critical temperature; of a chamber or extraction cell with thermal control (7) in which the natural source to be extracted is deposited; of two chambers or separating cells with thermal control (11 and 15) in which the solutes or part of the solutes extracted by the supercritical fluid are recovered; of three valves (9, 13 and 17) that regulate the pressure in the extraction cell and in the two separating cells and of a system that allows adding a polar solvent that acts as a polarity modifier to the supercritical fluid. This system is formed in turn by a container (20) where the polar solvent is located and by a pump (21) that allows it to be added to the supercritical fluid. It also consists of a container (19) where the aroma components are recovered either by means of a cold trap or by means of an adsorbent.

Figure 2. Chromatogram of the SI fraction of the first separator. HPLC analysis. 1 all trans- β-carotene, 2 and 3 cis-lycopene, 4 all-trans-lycopene.

Figure 3. Chromatogram of the SI fraction of the first separator. HPLC-Masses Analysis. 1 and 2 oxygenated derivatives of lycopene, 3- lycopene.

Figure 4 Chromatogram of fraction S2 of the second separator. HPLC analysis. 1 lutein, 2 α-tocopherol, 3 cis-phytoene, 4 and 7 cis-phytofluene, 5 all trans-phytoene, 6 all trans-phytofluene, ζ-carotene, 9 all trans-β-carotene, 10-13 cis-lycopene , 14 all transicopene.

Figure 5 Chromatogram of fraction S2 of the second separator. HPLC Analysis - Masses. 1 γ-tocopherol, 2 β-tocopherol, 3 α-tocopherol, 4 stigmasterol, 5 β-amyrin, 6 fagarsterol, 7 α-amyrin, 8 phytoene, 9 phytofluene, 10 phytoene isomer, 11 β-carotene, 12 lycopene.

EXAMPLE OF EMBODIMENT OF THE INVENTION Example 1

The procedure is applied to four tomato varieties Daniela, Rambo, Pera and Pitenza. The lycopene content was determined by spectrophotometry according to the method described by Hakala and Heinonen (Hakala SH and Heinonen IM, 1994. "Chromatographic Purification of Natural Lycopene" J. Agrie, Food Chem., 42, 1314-1316). Table 1 shows the lycopene contents of each of the tomatoes used. Except for the tomato of the Pera variety, the lycopene is found mostly in the skin Table 1. Lycopene content of tomato varieties. (% by weight of sample)

Starting from 55 g of raw material (whole tomato, skin or pulp) lyophilized, they are introduced into the extraction cell (Fig. 1 (7)) and extracted at 35 MPa and 40 ° C. In the first separating cell (Fig. 1 (11)) the SI fraction is collected at 15MPa and 50 ° C. In the second separating cell (Fig. 1 (15)) the fraction S2 is collected at 6MPa and 25 ° C. The processing time was from 6 h. Table 2 shows the percentages of extracted lycopene and those that are not extracted in the waste.

Table 2. Percentage of extracted and residual lycopene

The percentage of lycopene extracted depends on the tomato variety. In general, except for the skin of the Daniela variety, there are good percentages of lycopene recovery. Lycopene appears predominantly in the first SI separator in the form of crystals smaller than 10 μm in size.

Example 2

It starts with 55 g of lyophilized tomato skin. The extraction is carried out at 35 MPa and 40 ° C. In the first separator (11 Fig. 1) the pressure is set at 15 MPa and the temperature at 50 ° C. A crystalline solid of intense red color and a small amount is obtained of a colorless liquid with an oily appearance (Sl). In the second separator (15 Fig.l) the pressure it is fixed at 6 MPa and the temperature at room temperature produces an intense red-orange liquid with an oily appearance (S2).

These fractions were analyzed by reverse phase HPLC using a C ₃ column or with a linear gradient according to the method of Gómez-Prieto et al. (Gómez-Prieto MS; Caja MM; Santa-María G. 2002 "Solubility in supercritical carbon dioxide of the predominant carotenes of tomato skin" J. Am. Oil Chem. Soc. In press). The quantification was carried out at 472 nm, 450 nm, 347 nm and 285 nm. The HPLC-Masses coupling was used for the determination of the lipid compounds present in the SI and S2 fractions. For the determination of triglycerides and free fatty acids, the GC method of Ruiz del Castillo et al. (Ruiz del Castillo ML; Dobson G .; Brennan R., Gordon S. 2002 "Genotypic variation in fatty acid content of blackcurrant seeds" J. Agrie, Food Chem., 50 (2), 332-335).

The SI fraction obtained in the first separator is formed by red crystals of less than 10 μm in size and a colorless liquid. Figure 2 shows the chromatograms of the HPLC analysis of the pigments of the SI fraction. As can be seen, the majority is the all trans-lycopene (peak 4) and small amounts of cis-lycopene and β-carotene isomers. The all-trans-lycopene accounts for 91.4% of the total carotenoids. The GC analysis of the lipid components, other than the carotenoids, of the SI fraction reveals that triglycerides are the majority (78%), the rest are sterols and esters of fatty acids. The HPLC-Masses analysis (figure 3) reveals that only lycopene is present, no peaks with mass spectra corresponding to triglycerides or sterols have been found, probably because they are in very small concentration. Figure 2 shows two peaks (1 and 2) corresponding to oxygenated derivatives of lycopene. However, these compounds do not appear or are in trace amounts in the quantitative analysis (figure 2), it is possible that said compounds originated in the manipulation of the sample. In summary, the SI fraction is formed mainly by carotenes (97.8% by weight), 1.6% by weight triglycerides and the rest esters of sterols and other lipid compounds. In the SI fraction, crystals of all trans-lycopene of less than 10 μm in size are obtained, with a purity of 91.4%. The fraction S2 obtained in the second separator is formed by a liquid with an orange-red color due to the carotenoids it contains. Figure 4 shows the chromatograms of the HPLC analysis of the pigments of the S2 fraction. As you can see, this fraction is formed by a mixture of carotenoids, with the majority being frans-phytoene (peak 5) and all-trans-β-carotene (peak 9). In this fraction, the amount of cis isomers of lycopene is appreciable (peaks 10-13). The ratio of all-trans-lycopene / cis-lycopene isomers goes from 10.8 for the SI fraction to 1.4 for the S2 fraction. Of note is the presence of lutein (peak 1) and α-tocopherol (peak 2) in appreciable concentrations. The HPLC-Masses analysis of fraction S2 (figure 5) confirms the presence of all the compounds indicated in figure 4. It also shows the presence of γ- and β-tocopherol (peaks 1 and 2), sterols such as stigmasterol (peak 4). ) and fagarsterol (peak 6) and appreciable amounts of α- and β-amyrin (peaks 5 and 7) that have antidepressant properties. GC analysis of fraction S2 reveals that triglycerides and free fatty acids and esterified account for 45% by weight of this fraction. In summary, fraction S2 is basically formed by a mixture of carotenoids, tocopherols and amirine dispersed in an oil formed by triglycerides and free fatty acids, with stearic acid being the majority.

Claims

1. A process to extract carotenoids from natural sources with a high content of lycopene characterized by using a fluid as a solvent under supercritical conditions so that the extraction and fractionation of the extract are carried out in a single stage, obtaining two carotenoid fractions, the first of them formed by practically pure all-trans-lycopene and the other formed by a mixture of carotenoids together with other lipid components.

2. A process according to claim 1, characterized in that the only stage of the process consists of the following steps; a) extraction of the lipid components from the natural source followed by b) a decrease in the density of the fluid loaded with the extracted compounds, causing the precipitation of all-trans-lycopene followed in turn by c) another decrease in the density carried out in the fluid loaded with the rest of the lipid compounds extracted, causing the precipitation of all the compounds present, except for the aroma components.

3. A process according to claims 1 and 2, characterized in that the supercritical fluid used as a solvent is carbon dioxide.

4. A process according to claims 1, 2 and 3, characterized in that the supercritical fluid used as a solvent contains a co-solvent or modifier.

5. A process according to claim 4, characterized in that the co-solvent is water.

6. A process according to any one of claims 1 to 5, characterized in that the natural source contains, among others, whole tomato fruit, tomato skin, tomato pulp or any of its mixtures.

7. A process according to any one of claims 1 to 5, characterized in that the natural source contains a natural product with a high content of lycopene, preferably watermelon, certain algae and biomass from the fermentation of n microorganisms, or any of their mixtures .

8. A process according to any one of claims 6 and 7, characterized in that the natural source comes from surpluses and by-products of the agri-food industry.

9. A process according to any one of claims 6 to 8, characterized in that the natural source is subjected to a drying process, preferably lyophilized, and subsequent grinding, obtaining a powder with a degree of humidity of less than 10%.

10. A process according to any one of claims 1 to 9, characterized in that the extraction is carried out at a pressure between 25 and 40 MPa, preferably between 30 and 35 MPa and at a temperature between 35 and 70 degrees Celsius, preferably between 40 and 65 degrees centigrade.

11. A process according to any one of claims 1 to 9, characterized in that the decrease in the density of the supercritical fluid used as a solvent, preferably supercritical carbon dioxide (CO ₂ -SC), loaded with the extracted compounds is carried out by decreasing pressure at values between 10 and 20 MPa, preferably between 12 and 18 MPa, and temperature variation of 5 to 10 degrees centigrade with respect to the extraction temperature, increasing or decreasing it.

12. A process according to claim 11, characterized in that a deep red precipitate originates and the supercritical fluid used as a solvent, preferably supercritical carbon dioxide (CO ₂ -SC), loaded with the most soluble extracted lipid compounds.

13. A process according to any one of claims 11 and 12, characterized in that the precipitate provided by the first fraction is formed by lycopene crystals with a size of less than 10 µm and a purity of greater than 85%, preferably greater than 90%, while the rest of the lipid components extracted are still present in the supercritical fluid used as a solvent, preferably supercritical carbon dioxide (CO ₂ -SC).

14. A process according to any one of claims 1 to 9, characterized in that the decrease in the density of the supercritical fluid used as a solvent, preferably supercritical carbon dioxide (CO ₂ -SC), loaded with the most soluble lipid components, is carried out by decreasing the pressure at values between 1.5 and 10 MPa, preferably subcritical, between 4 and 6 MPa, optionally the temperature can be varied, preferably room temperature.

15. A process according to claim 14, characterized in that a precipitate with an oily appearance of red-orange color and CO ₂ gas originates which has in suspension the aroma components.

16. A process according to any one of claims 14 and 15, characterized in that the oily red-orange precipitate that constitutes the second fraction is formed by carotenoids in proportions by weight greater than 55%, preferably greater than 70%, being the majority β-carotene, phytoene, phytofluene and lycopene. In addition, there are appreciable amounts of tocopherols, between 15 and 25%, α-tocopherol being the majority, and other bioactive lipid components such as amirin, a compound with anti-inflammatory and antidepressant properties, in proportions between 0.1 and 5%.