MXPA99009568A - Process for obtaining concentrate of xanthophylls of high purity - Google Patents

Abstract

An industrial process for obtaining xanthophylls concentrates of high purity starting from vegetal extracts, which comprises the vegetal extracts refining by means of a treatment with a diluted alkali, followed by a treatment with a diluted organic or inorganic acid, eliminating part of the impurities, obtaining a refined extract;saponification of the refined extract by means of an aqueous solution strongly alkaline;treating the saponified diluted mass by means of an organic or inorganic acid, adjusting the pH between 4 and 7, in order to separate a xanthophylls concentrate;and extracting remnant impurities of the concentrate, by means of hexane.

Description

PROCESS TO OBTAIN CONCENTRATES OF HIGH PURITY XANTOPHILS BACKGROUND OF L? INVENTION: A FIELD OF THE INVENTION The present invention relates to an industrial process for obtaining high purity xanthophyll concentrates for human or animal consumption, from plant extracts and, more specifically, to a process of refining plant extracts using a treatment with diluted alkali followed by a treatment with diluted acid. B. DESCRIPTION OF THE RELATED TECHNIQUE Carotenoids are natural pigments that are widely distributed in the animal and plant kingdoms. They include the carotenoids, which are hydrocaitronic carotenoids, such as: ß-carotene, lycopene, among others, and xanthophylls that are oxygenated carotenoids such as: lutein, zeaxanthin, capsanthin, capsorrubin, astaxanthin, bixin, crccetin, among others. .

Carotenoids are produced naturally on a large scale, enccrrtpándose plants, microalgae, fungi, and bacteria. Animals do not have the capacity to synthesize carotenoids, and only take advantage of natural lilies for various purposes, among others to acquire color (birds and fish), or to fulfill metabolic and reproductive functions (crustaceans). In recent years, a great variety of research has been documented, indicating that some carotenoids, such as lutein and zeaxanthin, among others, have beneficial properties to humans. They emphasize their character as natural antioxidants which reduce the risk of degenerative diseases of tissues such as cancer; and act as preventive of macular degeneration in adults. An abundant and varied diet of feces and crisp vegetables should generally be sufficient to satisfy the requirements of said carotenoids by the man. However, at present, the human diet often lacks the adequate amount of lutein and zeaxanthin and / or other carotenoids. It is for this reason very desirable to have alternate or concentrated concentrators of high purity carotenoids. Lutein and zeaxanthin occur naturally in vegetables such as spinach, broccoli, peas, Brussels sprouts, pumpkins, as well as in fresh fruits such as mango, papaya, peaches and oranges, among others, and in plants such as alfalfa. . In some vegetables, xanthophylls are found in their free form. However, in most cases they are found in esterified forages; Fatty metered: myristic, lauric and palmitic, among others. In order to take advantage of said xanthophylls, the organism hydrolyzes them so that they can be absorbed and subsequently metabolized.

In the last decades, the cultivation of the cempasuchil (Tagetes Erecta) plant whose flowers have a high content of lutein and a lower proportion of zeaxanthin has been generalized worldwide. These xanthophylls are the natural source most used by the industry to make pigment foods for birds (chickens and chickens). In recent years, there has been a growing demand to reconcile the diet of man with said xanthophylls. For this reason it is very important to develop viable processes to axicentrate and purify xanthophylls for human consumption, such as lutein and zeaxanthin, among others. The works of Tcyczkowski and Hamilton reported in Foulby Science 70 (3): 651-654, 1991, isolate and crystallize the lutein (and zeaxanthin) of a saponified cc? Sntrado of oleoresin from cempasuchil, by means of a non-scalable process at industrial level, using solvents capable of leaving occluded or trapped residues in said crystals.

The use of methanol-type solvents, or halogenated organic solvents such as dido-methane or dichloroethane, involves crystallization and recrystallization processes, low temperatures, etc., to obtain high-purity lutein crystals. The use of solvents with a high level of toxicity requires of expensive elaboration equipment and high sophisticacton grade, which results in processes that could be unviable on an industrial scale, as in North American Patent No. 5,382.71 of Khachik et al, 1995. In North American Patent No. 5,643,564 issued to Ausich et al, 1997, it is stated that " Surprisingly, they erred that when saponifying the oleoresin of cempasuchil with an aqueous alkali diluted with propylene glycol, lutein crystals appear. It is corroded that the fatty acid diesters of xanthophylls are soluble in solvents related to fats and non-polar solvents such as hexane, precisely because of the affinity between the fatty acid chain and hydrocarbon-type solvents. When hydrolyzing xanthophylls and therefore losing their affinity to aliphatic solvents, their solubility in hydrocarbon-type solvents, or in aqueous media, is extremely low; being highly soluble in polar solvents such as ketones, alcohols, chlorinated solvents, etc. By means of the process of the present invention we have been able to obtain high purity xanthophyll corioentries in a simple manner, using non-toxic reagents and of low danger in their handling, without requiring extreme conditions or expensive equipment. Starting from the principle that using the same solvent (in this case hexane) with which the extraction of the esterified xanthophyls that are found in the vegetal matter (oleoresin) is carried out, and after a simple procedure by means of which they are insolubilized. mentioned xanthophylls, all the impurities and foreign materials (allts which were extracted with hexane) are separated from the xanthophyll concentrate using again hexane.

As we will see later, this process allows corvctrations of high purity lutein and zeaxanthin to be treated by oleoresins of cempasuchil flower (Tagetes Erecta) or capsantinayrapsoiTubiriadealteconcen ^ of red chili and / or paprika (Capsicum Annum). The novelty of this process is that, in the previous art, in this case the impurities are eliminated in the successive steps of purification, with the consequent enrichment of the xanthophylls. While in the other processes or methods reported, xanthophylls are selectively extracted from the mass by high-risk health solvents or use more expensive processes at very low temperatures, as well as crystallizations and recrystallizations in which oojmen men7iassustaixia.es. In this process to concentrate and purify xanthophylls such as lutein, zeaxanthin, capsanthin and capsorubin, among others, from plant extracts, it is a Jerrer efficient, economical and clean sofrer process. SUMMARY OF THE INVENTION The process of the present invention begins with a first stage of oleoresin refining consisting in the elimination of undesirable components, such as: free fatty acids, gums, waxes, phsphatides, lipids, dore-rows, compounds volatile, etc., and in the deodorization of it. This refining process is carried out by treating the material with a diluted alkaline solution, and carrying out a separation by means of ceritrifugadon. Subsequently an acid treatment is carried out, using a solution of diluted acid and carrying out a subsequent separation by centrifugation. The xanthophylls are crushed in the refined oleoresin, so the second stage of the present invention is the saponification of the xanthophylls to be released from the fatty acids, using a highly alkaline aqueous solution, in the presence of ernulsifiers and antioxidants. It should be noted that the present invention is carried out saponifying without using alcohols and / or organic solvents. Later the third stage of the invendón involves the treatment of the saponified extract that contains the xarrtofilas.diluyencto extract sapOT and treating it with dilute acid to take it to a slightly acidic pH; A series of aqueous washes is then carried out to eliminate acid residues and impurities of sodium and / or potassium that may be present; After the concentrate of xanthophylls the moisture is removed with temperature and high ford. In the fourth stage, the dry concentrate is extracted with hexane to eliminate permanent impurities such as soaps of fatty acids and / or free acids, as well as non-polar impurities still present. In the fifth stage, the solvent is removed by decanting and post-recovery recovered by porevaporadón. The concentracbtdexartsfilasceal next stage. During the sixth stage, the traces of residual solvent with heat and artifact are removed to the high purity xanthophyll corvctrate. it is stabilized and standardized, so that it can later be microencapsulated with a coating. The product thus obtained is highly pure with a content greater than 90% of total carotenoids, and with a concentration of xanthophylls greater than 95%. If higher purity is required, it can be obtained by repeating the previous purification process. It is therefore a prindpal objective of the present invention to propose a process for the procurement of high purity xanthella concentrates, from plant extracts (oleoresins). It is also a prindpal objective of the present invendón, propordonar a process of obtaining of concentrates of xantofilas of high purity, of the nature previously mendonada, that induces a refining stage to eliminate a substantial part of the impurities, for subsequent treatments. It is still a prindpal objective of the present invention to provide a process of obtaining high purity xanthophyll co-concentrates., of the previously mendonada nature, by means of depuradón, saponificadón, addificadón, and extracdón with hexane. It is also a prindpal objective of the present invention to provide a process of obtaining high purity xanthophyll concentrates, of previously merxonated nature, which has, among others, the following advantages: • Being a process to produce a higher xanthophyll concentrate. purity and oorxsr ^ than those of previous art. • To be a very profitable process, since during the procedure there is no considerable reduction of xanthophylls. • It is applicable to any quality of oleoresin and / or raw material • The previous process of refining the oleoresin guarantees a rts >; ycr purity in the produces • The operations are sent, and any operator can carry them out. • It's fast. It has short operating times • No sophisticated process and cartridges are required. • The procedure is environmental and ecological due to the re-utilization and recovery of the only solvent used. • Highly toxic or harmful materials are not used.

The solvent is reused. • It is a reproduced process. • B obtained product can be used in farmland for arta purity consorption, it can also be used in the pharmaceutical and cosmetics industry. • It is a process where the obtained product is high pure and corrosive. Used for dosing and formulation of minor corintronic products (pharmaceuticals). • The process of extracting impurities from the concentrated xanthophyll concentrate, by means of the acid, alkaline, neutral and non-polar solvents (hexane) guarantees greater purity in the final product. These and other objectives and advantages of the present investment will be evident to Ice experts in the field, of the following detailed description of the invention, and with reference to specific examples of the same. DETAILED DESCRIPTION OF THE INVENTION The process for the obtaining of concrertrados cte xantofilas cte alteration purity, c ^ invendón begins with: a first refining stage of the oleoresin that consists in the elimination of the undesirable components as the free fatty acids, gums, waxes, fbsratides, lipids, dorophylls, volatile compounds, etc., and in the deodorization thereof; this refining process is carried out by treating the plant extract (deorresin) with a dilute alkaline solution such as KOH, NaOH, CaCOa Nq ^ Oa KzCCfey / or combination of these, this solution having a ratio proportional to the content of present in the extract, in a molar ratio of adde: alkali between 1 : 0.5 to 1: 1, preferably 1: 0.5; the diluted alkaline treatment requires intense mixing of the mixture at temperatures of 25 to 90 ° C, preferably at 00 ° C, for a period of 1 to 240 minutes, preferably 30 minutes, then a phase separation is carried out, by centrifugation; the treatment with alkali is followed by a treatment with organic or inorganic acid, using a dilute solution of an acid such as acetic acid, phosphoric acid, hydroxycitric acid, etx, among others, in a proportion of 0.2 to 1.5% by volume, preferably 1%; the dilute acid treatment requires intensive stirring of the mixture at temperatures of 25 to 90 ° C, preferably at 40 ° C, for a time of 1 to 240 minutes, preferably 30 minutes, a subsequent separation of the mixture is subsequently carried out. the phases formed, by means of ceritrirugadón; The second stage of the present invention involves the saponification of the refined oleoresin, desgomated and ctesodorized, being mixed with an aqueous alkaline solution such as, KOH, NaOH in a proportion of between 20% to 60%, preferably 45% in weight on the refined extract, preferably in the presence of emulsifiers and antioxidants to avoid the loss of xanthophylls; The reaction mixture is kept in an inert atmosphere, such as Na CO2, helium, etc. at an atrnospheric pressure, and at a temperature between 40 ° C and 120 ° C, preferably 90 ° C, for a period of time of 1 to 48 hrs., preferably of 8 hrs, until the total saponification of xanthophylls is completed; it is important to note that in this process of saponification no alcohol is used, nor organic solvents, nor mixtures of these, unlike Ncrtearnerica Nos. 5,382,714 and 5648,564; with the aqueous saponification process, xanthophyll crystals are obtained without the need to carry out a crystallization process, nor to lower the temperature for obtaining the crystals, as indicated in US Pat. No. 5,382,714; when the saponification has reached its end, it is more than 95% of free xanthophylls, the mixture is cooled between 40 and 60 ° C, preferably at 50 ° C; 5 the sapchnified extract is diluted in water, in a soap: water ratio of between 1: 1 to 1: 5, preferably a relaon of 1: 3, stirring for 30 min .; subsequently the dough is brought to a pH between 4 and 7, preferably 5, with a dilute aqueous solution of acid, such as acetic acid, H 3 PO and stirring for a period of 1 hour, it should be noted that during the addition of the acid solder there are no increases 10 consicterablescte lamperperaturaen lamezda; this process of pH adjustment favors the insolubility of xanthophylls in hexane, preventing the elimination of impurities with affinity to this solvent; Specifically, the aqueous portion, which contains impurities of the alkali and / or polar impurities formed during the saponification process, is separated by decantation; 15 alcor? »Ntra ± > ctexartcfilasselere ^ of the washing water is neutral, completely eliminating the adde and polar impurities .; the amount of washings is variable and can be from 2 to 8 washes, preferably 4; Acid-free xanthophyll concentrate is dried at high vap between 5 and 26 inches of Hg, preferably 24 inches of Hg, at temperatures of 40 to 90 ° C, preferably 20 50 ° C, until a humidity of less than 10 is obtained. %; The dry xanthophyll concentrate is subjected to several extractions with hexane, in a hexane ratio of between 1: 1 to 1:10, preferably 1: 8, this extraction is carried out to extract the non-polar impurities, such as they are soaps of fatty acids and / or free acids, as well as other impurities related to hexane that may be present; In the extractions, intense agitation is required, temperatures of 25 to 60 ° C, preferably of 40 ° C, as well as a period of 1 to 240 min., preferably of 30 min., at atmospheric pressure, once the time of Extraction should be left at rest for 1 to 4 hours, preferably 2 hours; the extractions with hexane are carried out until the coloradon in the solvent disappears, between 2 and 10 extradrons, preferably 6; during this procedure it is important to note that the amount of extracted xanthophylls is minimal, and in addition they can be recovered from the solvent later, so that the loss of xanthophylls mediated by this process is very low; the separation of the hexane is carried out by decanting once the extiations and the rest are finished; the concentrate of xanthellae is sedimented in the bottom of the reactor, this way it is avoided that it is sealed with the solvent; the solvent decanted is evaporated with temperature and high ford to achieve its total recovery, as well as the separation of the impurities that it has extracted; It should be noted that the processing time of this stage can be considerably reduced with the use of a centrifuge; the residual hexane in the xanthofyls concentration is recovered by filtering at high ford, in rotary infiltrate; the hexane distilled above, as well as that recovered by filtration, is reused for similar processes, which causes the cost per process of this invention to be reduced remarkably; Subsequently, the concentration of xanthophylls with high purity is reduced at reduced pressure and at temperatures between 25 ° to 60 ° C, preferably 50 ° C; The dried xanthophyll oxide is standardized, stabilized and formulated. The corsair of purely xanthophylls is thus ready for the various application processes. The following examples are presented to illustrate, but not limit, the scope of the invention. EXAMPLE No. 1 Refinadon: 400 kg of cempasúchil flower oleoresin with a concentration of 90,000 ppm (AOAC), and with a 12% loading, is charged to a reactor and the temperature is raised to 40 ° C, and it is shaken gently, later it is added 400 Kg of aqueous solution of N 2C? 3 diluted to 2.5%, and it is stirred for 5 min, the agitation is stopped and the mixture is fed to a caitrifuge to separate the aqueous portion; The centrifuged oil phase is then charged to the reactor and stirred, then 400 Kg of phosphoric acid diluted at 1% is added, the contents of the reactor are stirred for 5 min. Then the mixture of the roaster is centrifuged to separate the aqueous portion, obtaining 285 kgs of refined oleoresin. Saponification. The refined oleoresin is charged to the reactor and 12Okg of 45% aqueous KOH are added, then the reactor content is heated to a temperature of 90 ° C, which is maintained for 8 hr. reaching a saponification percentage higher than 95.5%. Purification.

Subsequently, the heating is suspended and the temperature is reduced to 50 ° C, without stopping the stirring, 1.200 kg of hot water at 50 ° C is added and the stirring is continued for 1 hr; Subsequently, 100 kg of 25% strength acetic acid solution was added to adjust the acetone solution in a reactor of 5, and stir for 30 min; the aqueous portion of acid is removed by decanting, then washed with water (pH 7) until the pH of the wash solution is neutral; elconcerttractoctexar? tofilas (171 kgs) essecactoayayudacteterrpaaturayalaltovado until redudr humidity to 8%; Then, 5 washes of 1,100 kg of hexane are made to the xanthophyll compound, the hexane residues in the corium are eliminated by high vacuum at a temperature of 50 ° C; The dry xanthophyll concentrate thus obtained gave the following results: Quantity 39,100 kgs Total xanthophylls (AOAC) 870,000 mg / kg Purity lutein + zeaxanthin (HPLC): 97% Moisture (Kari Fischer) 8% As can be seen in this example, a product highly concentrated in xanthophylls and of a high purity (HPLC) is obtained due to the elimination procedures of undesirable components, from the first raw material to the obtained xanthophyllaccanter, having a pigment loss less than 5.5%, during the whole process. In this example, up to 94.5% of xanthophyll concentration on dry basis is obtained in the final product.

EXAMPLE No.2 Refinadón. 100 kg of flower oleoresin, with a 120,000 ppm ccncantradon (AOAC), with acidity of 14%, is charged to a reactor and the temperature is raised to 40 ° C, and it is stirred gently; subsequently, 100 kg of aqueous solution of NaCl2 diluted to 2.9% is added and the mixture is stirred for 5 minutes, the agitatedon is stopped and the mixture is added to an intestine to separate the aqueous portion; The oily phase is then charged to the reactor and stirred, then 100 Kg of 1% diluted phosphoric acid are added, the reactor content is stirred for 5 min., then the reactor mixture is centrifuged to separate the portion water, obtaining 71 kg of refined oleoresin. Saponrficadón. The refined oleoresin is charged to the reactor and 30 kg of 45% aqueous KOH are added; The contents of the roaster are then heated to a temperature of 90 ° C, which is maintained for 8 hours. reaching a percentage of saponrficadón higher than 95%. Purification. The skull is then suspended and the temperature is reduced to 50 ° C; without stopping the adidone treatment 300 Kgs of hot water at 50 ° C and stirring is continued for 1 hr, then 25 kgs of 25% acetic acid solution is adhered to adjust the aqueous solution in the reactor to a pH of 5, and stirred for 30 min; the aqueous portion of acid is eliminated by decanting, then washed with water (pH 7) until the pH of the wash solution is neutral; the ta? tracto? ta? ta? las (42 kgs) is dried with help of temperature and high vacuum to reduce the humidity to 10%; Subsequently, 5 washes of 270 Kg of hexane were made to the xanthophyll concentrate, the hexane residues in the oranotrich are removed by high vacuum at a temperature of 50 ° C. The dry xanthophyll column, thus obtained, gave the following results: Quantity 13.4 kgs Total xanthophylls (AOAC) 845,000 mg / kg Purity lutein + zeaxanthin (HPLC): 96.5% Moisture (Kart Fischer) 10% As can be seen in this example , a product highly concentrated in xanthophylls and of a high puteza (HPLC) is obtained. Due to the elimination process of undesirable components, from the original raw material to the obtained xanthophylls, having a pigment loss of less than 6% during the whole process. In this example we obtain up to 93.8.5% of ccncenti ^ cVi cte xartofilas on dry basis in the final product. It is finally necessary to note that in the foregoing document, specific reference is made to hexane as a selective solvent for this process, so that it may be possible to use some other type of liquid solvent of a similar chemical nature.

Claims (22)

1. REMNDICATIONS: 1. A process to obtain xanthophyll concentrates of high purity from extracted vegetale, the improvement comprising: refining plant extracts by means of a treatment with a diluted alkali, followed by a treatment with a diluted organic or inorganic acid, In order to eliminate impurities and get a refined extract.
2. 2. The process in accordance with claim 1, characterized in that the plant extract comprises oleoresins with a flower of cempazuchil (Tagetes Erecta); red chile oleoresins and / or paprika (Capsicum Annum); oleoresins of saponified and isomaized flower; extracted from Haeariatcccocus Pluvialis; extract of the fruit of the Lydum Barbarum plant; extracts of Bixa Orellana; extracted from Crccus Sativus; or mixtures thereof.
3. 3. The process according to claim 1, wherein the dilute alkali is selected from the group consisting of alkali metal hydroxides; hydroxides of alkaline earth metals; alkali metal carbonates; and alkaline earth metal carbonates.
4. 4. The process according to claim 1, characterized in that the alkali is present in a molar relation to the adde of the vegetable extract, from 1: 0.5 to 1: 1.
5. 5. The process of compliance with claim 1, characterized in that the organic or inorganic acid is selected from the group consisting of phosphoric acid, acetic acid, hydroxycitric acid, etc.
6. 6. The process according to claim 1, characterized in that the organic or inorganic acid is present in a concentrate of 0.2 to 1.5% by volume.
7. 7. The process according to claim 1, characterized in that it comprises saponifying the refined extract by means of an aqueous alkaline solution.
8. 8. The process according to claim 1, characterized in that it comprises treating the saponified mass diluted by an organic or inorganic acid.; adjust the pH between 4 and 7 to separate a xanthophyll detector; remove excess acid and fbrrnate salts by aqueous washing and drying, and separate a concentrate of xanthophylls.
9. 9. The process of conformity with rejection 1, caraderized by means of extracting remaining impurities from the corcentrate, by means of hexane.
10. 10. The process of this confonriidadc? Xi the ref indit ^ ^ isomerizar the saponified mass, iscrnerizando lutein in zeaxanthin, in order to obtain a ccacaitrado of xantofilas of alteration purity.
11. 11. The process according to claim 1, wherein the xanthophyll concentrates of different purity comprise trans lutein; trans zeaxanthin; trans capsanthin; capsorrubin; β-caratene; b? xina; crocetin; astaxanthin, among others; or mixtures of these.
12. 12. The process according to claim 1, characterized in that the dilute alkaline treatment and dilute acid are carried out with stirring at a temperature of between 25 ° C to 90 ° C, for a time of about one minute to 4 hours.
13. 13. The process of conformation with claim 1, characterized in that the dilute alkaline treatment and diluted acid is carried out with agitation at a temperature of 40 ° C, for 30 minutes.
14. 14. Process for obtaining xanthophylls of different purity from vegetal extracts, caraderizado because it comprises: refining the extra vegeteles by means of a treatment with a diluted alkali, followed by a treatment with a dilute organic or inorganic acid, eliminating part of the impurities and obtained a refined extract; saponifying the refined extract by means of a strongly alkaline aqueous solution; dilute the saponified mass and treat it with an organic or inorganic acid by adjusting the pH between 4 and 7, in order to separate a xanthophyll caxentrate; remove excess acid and salts formed by aqueous washing and drying; and extract remaining impurities from the concentrate, by means of hexane.
15. 15. The process according to claim 14, characterized in that the refining step comprises treating the plant extract, to eliminate impurities.
16. 16. The process according to claim 14, characterized in that the hexane is readjusted and reused.
17. 17. The process according to claim 14, characterized in that the xanthophyllates have a concentration of up to 98% of xanthophylls, according to AOAC and a purity higher than 95% by HPLC.
18. 18. The process of compliance with claim 14, characterized in that the purity of xanthophylls by HPLC is greater than 95%.
19. 19. The process according to claim 14, caradertzacto because hexane extracts rare impurities of non-polar origin.
20. 20. The process according to claim 14, characterized in that the treatment of the saponified mass with acid is carried out by diluting the saponified mass with water, in a ratio of mass: ag? Racteaproxima-tenr? Ente1: 3, at a temperature of 40 to 60oC, for 60 minutes with agifadon in order to separate an aqueous phase and an oil phase; wash in order to eliminate residues of acid and impurities, and separate and dry the oil phase, or xanthophyll concentrate.
21. 21. The process according to claim 14, characterized in that the extraction step with hexane is carried out at room temperature or higher; with a hexane relase: concentrate of approximately 1: 1 to 10: 1
22. 22. The process according to claim 14, characterized in that the xanthophyll concentrate of high purity is filtered in order to eliminate the hexane, dried at high ford, stabilized , standardized and formulated.