EP0137862B1 - Process for the preparation of fatty material - Google Patents

Process for the preparation of fatty material Download PDF

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Publication number
EP0137862B1
EP0137862B1 EP83110241A EP83110241A EP0137862B1 EP 0137862 B1 EP0137862 B1 EP 0137862B1 EP 83110241 A EP83110241 A EP 83110241A EP 83110241 A EP83110241 A EP 83110241A EP 0137862 B1 EP0137862 B1 EP 0137862B1
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Prior art keywords
oil
pips
solvent
flakes
polar
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EP83110241A
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German (de)
French (fr)
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EP0137862A1 (en
Inventor
Helmut Traitler
Heike Winter
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Societe des Produits Nestle SA
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Societe des Produits Nestle SA
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Priority to DE8383110241T priority Critical patent/DE3373673D1/en
Priority to AT83110241T priority patent/ATE29733T1/en
Priority to EP83110241A priority patent/EP0137862B1/en
Priority to ES536678A priority patent/ES536678A0/en
Priority to DK487084A priority patent/DK169557B1/en
Priority to JP59214026A priority patent/JPS60104195A/en
Publication of EP0137862A1 publication Critical patent/EP0137862A1/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/06—Production of fats or fatty oils from raw materials by pressing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
    • C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids

Definitions

  • the present invention relates to a process for the preparation of fatty substances from fruits of the genus Ribes.
  • Gamma-linolenic acid is an essential fatty acid which is metabolized by the body into prostaglandins via dihomo-gamma-linolenic acid and arachidonic acid (5,8,11,14-êicosa- tetraene), which is itself a constituent of cell membranes while alpha-linolenic acid does not contribute in the same way to this metabolic process.
  • the conversion of linoleic acid ⁇ gamma-linolenic acid in the tissues is incomplete (4-20%) compared to 90-98% for the transformation gamma-linolenic acid - 7 arachidonic acid) and may even be non-existent (e.g. for the cat) in case of absence or inactivation of the enzyme A-6-desaturase.
  • a lack of essential fatty acids leads in fact to a nutritional deficiency affecting all the metabolic processes mentioned above and which can lead to biochemical disorders or to organic lesions (e.g. coagulation disorders, dermatological lesions, endocrine disorders, myocardial damage, liver, joint, neurological and mental disorders).
  • biochemical disorders or to organic lesions e.g. coagulation disorders, dermatological lesions, endocrine disorders, myocardial damage, liver, joint, neurological and mental disorders.
  • gamma-linolenic and arachidonic acids as therapeutic and nutritional agents p. ex. in FR-A-2197605 and 1603383, gamma-linolenic acid being of synthetic origin or extracted from evening primrose seed oil (Oenothera) or officinal borage (Borage officinalis).
  • FR-A-2255055 relates to cosmetic or pharmaceutical compositions based on raspberry seed oil, the anti-inflammatory activity of which is mentioned without indicating its composition.
  • the oil being preferably extracted with chloroform (polar solvent), the anti-inflammatory activity is probably due to the presence of minor components.
  • An analysis of this oil also showed that it contained approximately 54% by weight of linoleic acid and 30% of alpha-linolenic acid but did not contain gamma-linolenic acid.
  • Hungarian Patent No. T 13226 mentions that the addition of a ground product or crude oil extracted from paprika seeds, tomatoes or currants to cosmetic products or table oils would inhibit their oxidation.
  • the extraction as provided does not allow the undesirable dyes and waxes to be separated in the products envisaged and the composition of the extract is not mentioned.
  • the fruit seed oils of the genus Ribes contain a significant percentage, at least 4% by weight of gamma-linolenic acid.
  • these seeds are available in large quantities in oil cakes from the pressing of fruit juices, the production of jams and jellies or fermentation musts from the production of spirits, liqueurs and schnapps, by-products. which were hitherto used as fuel or as fodder.
  • the fatty substances come in practice from blackcurrant (Ribes nigrum), currants (Ribes rubrum), gooseberries (Ribes ova-crispa or grossularia) or from hybrid fruits of these species.
  • blackcurrant Ros nigrum
  • currants Ros rubrum
  • gooseberries Ros ova-crispa or grossularia
  • hybrid fruits of these species One can of course use a mixture of these fruits.
  • the lipid content of the above-mentioned by-products is 12 to 30% by weight depending on the raw material.
  • the lipid phase in turn contains 4 to 19% by weight of gamma-linolenic acid.
  • the seed oil of these fruits consists of triglycerides of the following fatty acids, by weight:
  • Blackcurrant oil which is preferred because of its high content of gamma-linolenic acid, also contains 1 to 2% by weight of unsatifiable bodies, such as aliphatic alcohols, hydrocarbons, tocopherols, squalene, P-sitostero , cam- pesterol and A-7 stigmasterol. Its density is 0.9215g / cm 3 (at 20 ° C) and its viscosity 28.3 mPa.s (28.3 centipoise) (at 20 ° C).
  • the term plant material used means the by-products mentioned above.
  • the raw material is generally in the form of highly colored oil cakes and containing the waxes associated with the seeds, waxes and dyes representing from 5 to 7% by weight of the crude oil that would be extracted therefrom, for example. ex. with hexane.
  • Waxes are saturated and monounsaturated esters of fatty alcohols and long chain fatty acids that are solid at room temperature. The waxes and dyes in question are not desired in an oil constituting the nutritive compositions.
  • a raw material of choice is the cake for pressing fruit juices, in particular blackcurrants. We dry it first p. ex. in air for about 1 hour at around 60 ° C. It is coarsely ground and sieved, so as to obtain particles of 1 to 1.5 mm, the sieving yield being 60 to 80% of the weight of the cake. It is advantageous to separate the seeds from the straws by gravity in an air stream or "elutriation" with a yield by weight of 80 to 90%.
  • the seeds are washed with a polar solvent in common use so as to rid them of waxes, dyes and free fatty acids.
  • a polar solvent for cosmetic applications, p. ex. methanol, isopropanol, acetone, ethanol or a mixture of these solvents or else a supercritical fluid p. ex. carbon dioxide under conditions which give it a polar character.
  • an authorized solvent p. ex. ethanol or supercritical carbon dioxide for food and pharmaceutical applications.
  • the seeds are washed with ethanol at reflux, either by batch, p. ex. a first time for approximately 2 hours and a second time for approximately 30-60 minutes, either continuously for approximately Z hours and then wring out the residue.
  • the seeds can be washed using p. ex. carbon dioxide at 250-350 b and 60-80 ° C in a continuous cycle, the solvent being recovered in gaseous form by reduction of the pressure, recompressed and recycled. It has been found that washing makes it possible to remove most of the coloring matters and waxes present in the films and around the seeds: in fact, the waxes are deposited by cooling from the alcoholic extract while the latter is very strongly colored.
  • the washed and drained seeds are treated with an antioxidant so as to protect their oil from oxidation during the subsequent stages.
  • an antioxidant there may be mentioned dilute aqueous solutions of ascorbic or benzolic acid or their sodium or potassium salts, for example an aqueous solution containing 30 to 50 ppm (parts per million) by weight of ascorbic acid, at a rate of 7-8% of the weight of the seeds used.
  • the protected seeds are pressed p. ex. by means of a continuous screw press under high pressure and up to 90% of the oil contained in the seeds is obtained according to the type of press used, the pressing conditions and the number of pressing cycles applied.
  • the pressing is followed by solvent extraction from the pressing cake.
  • Protected and dried seeds are flaked on a flattening cylinder. This shaping avoids clogging and facilitates the subsequent extraction of the oil by giving the product porosity allowing good penetration of the solvent, and the flakes in particular resist crushing.
  • the flakes are heated to 80-90 ° C and pressed under a pressure of 490-785 b (500-800 kg / cm 2 ), maintaining the temperature of the press head at a value below 90 ° C . In this way, 50 to 60% of the oil contained in the seeds is obtained.
  • the pressing cake has a density of 0.58 to 0.65, about twice the density of the flakes and can be appropriately percolated with the extraction solvent.
  • the pressing cake is ground and the ground residue is extracted.
  • the residual oil is extracted with a non-polar solvent, e.g. ex. hexane in an amount of 200 to 250% by weight of hexane relative to the residue.
  • a non-polar solvent e.g. ex. hexane in an amount of 200 to 250% by weight of hexane relative to the residue.
  • liquid carbon dioxide or preferably supercritical carbon dioxide can also be used in this step, under conditions where it is weakly polar, e.g. ex. at 200-300 bar and 40-60 ° C.
  • p. ex. supercritical carbon dioxide in the washing step and in the subsequent extraction step or in only one of these steps, the other being carried out with p. ex. ethanol, respectively hexane.
  • the pressure oil and the extraction solution are combined. It is possible, although these measures constitute only preferred options, to neutralize the mixture in order to remove the residual free fatty acids, possibly after having partially evaporated the solvent, p. ex. in the case of hexane so that the solution contains approximately 10% by weight of oil, by concentrated sodium or potassium hydroxide (2N), cool it to approximately 0-4 ° C for approximately 24 hours and filter it at this temperature so as to completely eliminate the residual waxes. Likewise, the following discoloration and deodorization are preferred options: lore the solution with an adsorbent p. ex.
  • activated charcoal or activated bleaching earths based on activated aluminum silicate such as montmorillonite or bentonite at a rate of 2-8% by weight relative to the oil used at 20-60 ° C. and then the solvent is evaporated.
  • the oil is then deodorized by steam entrainment at 140-220 ° C and preferably at approximately 180 ° C under a vacuum of 0.75 mb (1 torr) or less.
  • the seeds are not washed beforehand (step a)) but the pressing is carried out directly followed optionally by extraction with a solvent from the pressing cake.
  • neutralization, elimination of waxes by decantation, discoloration and deodorization as indicated above (steps f) to i)) are essential for obtaining a pale yellow refined oil.
  • the oil freed from waxes and free fatty acids is saponified with an alkali hydroxide, for example potassium hydroxide in methanol / water at a concentration of approximately 11%, the salts obtained are acidified.
  • an alkali hydroxide for example potassium hydroxide in methanol / water at a concentration of approximately 11%
  • the salts obtained are acidified.
  • a mineral acid e.g. ex. 2N sulfuric acid
  • the fatty acids liberated by hexane are extracted, the organic phase is separated and dried p. ex. by addition of sodium sulfate.
  • the organic phase is fractionated by high performance liquid chromatography, by passage over columns of silica gel loaded with silver nitrate and elution preferably with a mixture of dichloromethane, toluene and diethyl ether 70/25/5 - 63 / 30/5 in isocratic mode, that is to say with recycling of the solvent mixture of fixed composition and a fraction containing approximately 60% by weight of gamma-linolenic acid and approximately 40% of alpha-linolenic acid is thus obtained. .
  • Almost pure gamma-linolenic acid can be isolated by performing high performance liquid chromatography with support on the C 8 or C 18 side in reverse phase with gradient of solvent mixture acetonitrile / water, methanol / water or isopropanol / water.
  • the fatty substances obtained according to the invention can be incorporated into nutritive compositions according to European patent application No. 92085.
  • the following example illustrates the invention. In it the parts and percentages are expressed in weight value unless otherwise indicated.
  • the previously washed seeds are sprayed with 14-16 water containing 30-50 ppm (parts per million) of ascorbic acid.
  • the treated seeds are dried at 70 ° C for 30-40 min and put into the form of flakes using a flattening roller mill.
  • the flakes are heated to 80-90 ° C for 30-40 min. These have a density of 0.35.
  • the flakes are pressed for 30-50 min in a continuous screw press under a pressure of 500-800 kg / cm 2 with a screw rotation speed of 10-20 revolutions / min while maintaining the head temperature of the press at 80-90 ° C.
  • 26-31 kg of oil are thus obtained (approximately 50-60% of the oil present in the seeds).
  • the pressing cake has a density of 0.60 which allows percolation without clogging during the subsequent extraction step. It is ground and extracted with 2 times 370-400 kg of hexane at reflux for 3 h. Then cool and filter. After evaporation of the hexane, 22 to 26 kg of additional oil are thus collected.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

1. A process for preparation of a fatty substance from pips of fruits of the Ribes genus, characterized by the following steps : a) washing the pips with a polar solvent or a supercritical fluid in a polar condition, b) treating the pips with an antioxidant in order to protect the oil contained therein against oxidation, c) forming the protected pips into flakes, d) pressing the flakes and collecting the oil, e) extracting the rest of the oil from the press cake with a non-polar solvent or a supercritical fluid in a slightly polar condition and the removing the solvent or the supercritical fluid.

Description

La présente invention concerne un procédé de préparation de corps gras à partir de fruits du genre Ribes.The present invention relates to a process for the preparation of fatty substances from fruits of the genus Ribes.

La plupart des huiles végétales contiennent les acides gras polyinsaturés linoléique (6,9-octadé- cadiénique) et alpha-linolénique (9,12,15-octadécatriénique). Seules les huiles des graines de houblon (Humulus), ce chanvre (Cannabis), de bourrache (borage) et d'onagre (Oenothera) sont connues pour contenir l'acide gamma-linolénique (6,9,12-octadécatriénique), l'onagre en étant la seule source disponible par ailleurs à un prix élevé.Most vegetable oils contain the polyunsaturated fatty acids linoleic (6,9-octadecadienic) and alpha-linolenic (9,12,15-octadecatrienic). Only the oils from the seeds of hops (Humulus), this hemp (Cannabis), borage (borage) and evening primrose (Oenothera) are known to contain gamma-linolenic acid (6,9,12-octadecatrienic), l evening primrose by being the only source available elsewhere at a high price.

L'acide gamma-linolénique est un acide gras essentiel qui est métabolisé par l'organisme en prostaglandines via l'acide dihomo-gamma-linolénique et l'acide arachidonique (5,8,11,14-êicosa- tétraénique), qui est lui-même un constituant des membranes cellulaires tandis que l'acide alpha-linolénique ne contribue pas de la même manière à ce processus métabolique. La conversion acide linoléique → acide gamma-linolénique dans les tissus est incomplète (4-20%) comparé à 90-98% pour la transformation acide gamma-linolénique -7 acide arachidonique) et peut même être inexistante (p. ex. pour le chat) en cas d'absence ou d'inactivation de l'enzyme A-6-désaturase.Gamma-linolenic acid is an essential fatty acid which is metabolized by the body into prostaglandins via dihomo-gamma-linolenic acid and arachidonic acid (5,8,11,14-êicosa- tetraene), which is itself a constituent of cell membranes while alpha-linolenic acid does not contribute in the same way to this metabolic process. The conversion of linoleic acid → gamma-linolenic acid in the tissues is incomplete (4-20%) compared to 90-98% for the transformation gamma-linolenic acid - 7 arachidonic acid) and may even be non-existent (e.g. for the cat) in case of absence or inactivation of the enzyme A-6-desaturase.

Un manque d'acides gras essentiels conduit en effet à une carence nutritionnelle affectant tous les processus métaboliques mentionnés plus haut et pouvant conduire à des désordres biochimiques ou à des lésions organiques (p. ex. troubles de la coagulation, lésions dermatologiques, troubles endocriniens, lésions myocardiques, troubles hépatiques, articulaires, neurologiques et mentaux). On voit donc l'intérêt que présente un apport d'acide gamma-linolénique pour la prévention ou pour le traitement de ces anomalies.A lack of essential fatty acids leads in fact to a nutritional deficiency affecting all the metabolic processes mentioned above and which can lead to biochemical disorders or to organic lesions (e.g. coagulation disorders, dermatological lesions, endocrine disorders, myocardial damage, liver, joint, neurological and mental disorders). We can therefore see the value of a gamma-linolenic acid contribution for the prevention or for the treatment of these anomalies.

On a mentionné la possibilité d'utiliser les acides gamma-linolénique et arachidonique comme agents thérapeutiques et nutritionnels p. ex. dans FR-A-2197605 et 1603383, l'acide gamma-linolénique étant d'origine synthétique ou extrait de l'huile de graine d'onagre (Oenothera) ou de bourrache officinale (Borage officinalis).Mention has been made of the possibility of using gamma-linolenic and arachidonic acids as therapeutic and nutritional agents p. ex. in FR-A-2197605 and 1603383, gamma-linolenic acid being of synthetic origin or extracted from evening primrose seed oil (Oenothera) or officinal borage (Borage officinalis).

De plus, FR-A-2255055 concerne des compositions cosmétiques ou pharmaceutiques à base d'huile de pépins de framboise dont on mentionne l'activité anti-inflammatoire sans en indiquer la composition. L'huile étant extraite de préférence au chloroforme (solvant polaire), l'activité anti-inflammatoire est vraisemblablement due à la présence de composants mineurs. Une analyse de cette huile a par ailleurs montré qu'elle contenait environ 54% en poids d'acide linoléique et 30% d'acide alpha-linolénique mais ne contenait pas d'acide gamma-linolénique.In addition, FR-A-2255055 relates to cosmetic or pharmaceutical compositions based on raspberry seed oil, the anti-inflammatory activity of which is mentioned without indicating its composition. The oil being preferably extracted with chloroform (polar solvent), the anti-inflammatory activity is probably due to the presence of minor components. An analysis of this oil also showed that it contained approximately 54% by weight of linoleic acid and 30% of alpha-linolenic acid but did not contain gamma-linolenic acid.

Enfin, le brevet hongrois No. T 13226 mentionne que l'addition d'un broyat ou de l'huile brute extraite à partir de pépins de paprika, de tomates ou de groseilles à des produits cosmétiques ou des huiles de table inhiberait leur oxydation. L'extraction telle qu'elle est prévue ne permet pas de séparer les colorants et les cires indésirables dans les produits envisagés et la composition de l'extrait n'est pas mentionnée.Finally, Hungarian Patent No. T 13226 mentions that the addition of a ground product or crude oil extracted from paprika seeds, tomatoes or currants to cosmetic products or table oils would inhibit their oxidation. The extraction as provided does not allow the undesirable dyes and waxes to be separated in the products envisaged and the composition of the extract is not mentioned.

On a constaté de façon tout à fait surprenante que les huiles de pépins de fruits de genre Ribes contenaient un pourcentage appréciable, au moins 4% en poids d'acide gamma-linolénique. De plus ces pépins sont disponibles en grandes quantités dans les tourteaux provenant du pressage des jus de fruits, de la fabrication des confitures et gelées ou des moûts de fermentation provenant de la production des eaux-de-vie, liqueurs et schnaps, sous-produits qui étaient jusqu'à présent utilisés comme combustible ou comme fourrage.It has been found quite surprisingly that the fruit seed oils of the genus Ribes contain a significant percentage, at least 4% by weight of gamma-linolenic acid. In addition, these seeds are available in large quantities in oil cakes from the pressing of fruit juices, the production of jams and jellies or fermentation musts from the production of spirits, liqueurs and schnapps, by-products. which were hitherto used as fuel or as fodder.

Selon l'invention, les corps gras proviennent en pratique du cassis (Ribes nigrum), des groseilles (Ribes rubrum), des groseilles à maquereau (Ribes ova-crispa ou grossularia) ou des fruits d'hybrides de ces espèces. On peut bien entendu utiliser un mélange de ces fruits.According to the invention, the fatty substances come in practice from blackcurrant (Ribes nigrum), currants (Ribes rubrum), gooseberries (Ribes ova-crispa or grossularia) or from hybrid fruits of these species. One can of course use a mixture of these fruits.

Le contenu en lipides des sous-produits mentionnés ci-dessus est de 12 à 30% en poids suivant la matière première. La phase lipidique contient à son tour de 4 à 19% en poids d'acide gamma-linolénique.The lipid content of the above-mentioned by-products is 12 to 30% by weight depending on the raw material. The lipid phase in turn contains 4 to 19% by weight of gamma-linolenic acid.

A titre indicatif, l'huile des pépins de ces fruits est constituée de triglycérides des acides gras suivants, en poids:

Figure imgb0001
As an indication, the seed oil of these fruits consists of triglycerides of the following fatty acids, by weight:
Figure imgb0001

L'huile de cassis qui est préférée à cause de sa teneur élevée en acide gamma-linolénique, contient en outre de 1 à 2% en poids de corps insapo- nifiables, tels que alcools aliphatiques, hydrocarbures, tocophérols, squalène, P-sitostéroi, cam- pestérol et A-7 stigmastérol. Sa densité est 0,9215g/cm3 (à 20 °C) et sa viscosité 28,3 mPa.s (28,3 centipoise) (à 20 °C).Blackcurrant oil, which is preferred because of its high content of gamma-linolenic acid, also contains 1 to 2% by weight of unsatifiable bodies, such as aliphatic alcohols, hydrocarbons, tocopherols, squalene, P-sitostero , cam- pesterol and A-7 stigmasterol. Its density is 0.9215g / cm 3 (at 20 ° C) and its viscosity 28.3 mPa.s (28.3 centipoise) (at 20 ° C).

L'invention concerne un procédé de préparation de corps gras à partir de pépins de fruits du genre Ribes, caractérisé par les étapes suivantes:

  • a) on lave les pépins avec un solvant polaire ou un fluide supercritique à l'état polaire et on élimine le solvant ou le fluide supercritique, cette étape étant facultative,
  • b) on traite les pépins avec un antioxydant de manière à protéger l'huile qu'ils contiennent de l'oxydation,
  • c) on met les pépins protégés sous forme de flocons,
  • d) on presse les flocons et on receuille l'huile, e) on extrait l'huile résiduelle du gâteau de pressage avec un solvant non polaire ou un fluide supercritique à l'état faiblement polaire puis on élimine le solvant ou le fluide supercritique.

Le procédé selon l'invention comporte de préférence les étapes supplémentaires suivantes, lesquelles sont indispensables lorsque l'étape a) précédente est supprimée mais constituent une option lorsque l'étape a) est maintenue:
  • f) on mélange l'huile de pression et une solution contenant l'huile "résiduelle de l'étape e) puis on neutralise le mélange pour en éliminer les acides gras libres résiduels,
  • g) on refroidit le mélange neutralisé, on le laisse décanter et on le filtre,
  • h) on décolore le filtrat par un adsorbant puis on élimine le solvant et
  • i) on désodorise l'huile.
The invention relates to a method for preparing fatty substances from fruit seeds of the genus Ribes, characterized by the following steps:
  • a) the seeds are washed with a polar solvent or a supercritical fluid in the polar state and the solvent or the supercritical fluid is removed, this step being optional,
  • b) the seeds are treated with an antioxidant so as to protect the oil which they contain from oxidation,
  • c) the protected seeds are put in the form of flakes,
  • d) the flakes are pressed and the oil is collected, e) the residual oil is extracted from the pressing cake with a non-polar solvent or a fluid supercritical in the weakly polar state then the solvent or the supercritical fluid is eliminated.

The method according to the invention preferably comprises the following additional steps, which are essential when the previous step a) is deleted but constitute an option when the step a) is maintained:
  • f) the pressure oil and a solution containing the residual oil from step e) are mixed, then the mixture is neutralized in order to remove the residual free fatty acids therefrom,
  • g) the neutralized mixture is cooled, allowed to settle and filtered,
  • h) the filtrate is discolored with an adsorbent and then the solvent is removed and
  • i) the oil is deodorized.

Selon l'invention, on entend par matière végétale mise en oeuvre les sous-produits mentionnés ci-dessus. La matière première est généralement sous forme de tourteaux fortement colorés et contenant les cires associées aux pépins, cires et colorants représentant de 5 à 7% en poids de l'huile brute qu'on en extrairait, p. ex. par de l'hexane. Les cires sont des esters saturés et mono-insaturés d'alcools gras et d'acides gras à longue chaîne solides à la température ordinaire. Les cires et colorants en question ne sont pas désirés dans une huile constitutive des compositions nutritives.According to the invention, the term plant material used means the by-products mentioned above. The raw material is generally in the form of highly colored oil cakes and containing the waxes associated with the seeds, waxes and dyes representing from 5 to 7% by weight of the crude oil that would be extracted therefrom, for example. ex. with hexane. Waxes are saturated and monounsaturated esters of fatty alcohols and long chain fatty acids that are solid at room temperature. The waxes and dyes in question are not desired in an oil constituting the nutritive compositions.

Une matière première de choix est le gâteau de pressage des jus de fruits, en particulier de cassis. On le sèche d'abord p. ex. à l'air pendant environ 1 heure à environ 60 °C. On le moud grossièrement et on le tamise, de manière à obtenir des particules de 1 à 1,5 mm, le rendement du tamisage étant de 60 à 80% du poids des tourteaux. On peut avantageusement séparer les graines des pailles par gravité dans un courant d'air ou «élutriation» avec un rendement en poids de 80 à 90%.A raw material of choice is the cake for pressing fruit juices, in particular blackcurrants. We dry it first p. ex. in air for about 1 hour at around 60 ° C. It is coarsely ground and sieved, so as to obtain particles of 1 to 1.5 mm, the sieving yield being 60 to 80% of the weight of the cake. It is advantageous to separate the seeds from the straws by gravity in an air stream or "elutriation" with a yield by weight of 80 to 90%.

Selon une forme d'exécution préférée du procédé, on procède au lavage des graines par un solvant polaire d'utilisation courante de manière à les débarrasser des cires, colorants et acides gras libres. Pour les applications cosmétiques, on peut utiliser p. ex. le méthanol, l'isopropanol, l'acétone, l'éthanol ou un mélange de ces solvants ou encore un fluide supercritique p. ex. le dioxyde de carbone dans des conditions lui conférant un caractère polaire. Pour les applications alimentaire et pharmaceutique, on utilisera un solvant autorisé p. ex. l'éthanol ou le dioxyde de carbone supercritique.According to a preferred embodiment of the process, the seeds are washed with a polar solvent in common use so as to rid them of waxes, dyes and free fatty acids. For cosmetic applications, p. ex. methanol, isopropanol, acetone, ethanol or a mixture of these solvents or else a supercritical fluid p. ex. carbon dioxide under conditions which give it a polar character. For food and pharmaceutical applications, an authorized solvent p. ex. ethanol or supercritical carbon dioxide.

A titre d'exemple, on lave les graines à l'éthanol au reflux soit par charges, p. ex. une première fois pendant environ 2 heures et une seconde fois pendant environ 30-60 minutes, soit en continu pendant environ Zheures puis en essore le résidu.By way of example, the seeds are washed with ethanol at reflux, either by batch, p. ex. a first time for approximately 2 hours and a second time for approximately 30-60 minutes, either continuously for approximately Z hours and then wring out the residue.

On peut en variante laver les graines en utilisant p. ex. le dioxyde de carbone à 250-350 b et 60-80°C en cycle continu, le solvant étant récupéré sous forme gazeuse par diminution de la pression, recomprimé et recyclé. On a constaté que le lavage permettait d'éliminer la plupart des matières colorantes et des cires présentes dans les pellicules et autour des pépins: en effet, les cires se déposent par refroidissement à partir de l'extrait alcoolique tandis que celui-ci est très fortement coloré.Alternatively, the seeds can be washed using p. ex. carbon dioxide at 250-350 b and 60-80 ° C in a continuous cycle, the solvent being recovered in gaseous form by reduction of the pressure, recompressed and recycled. It has been found that washing makes it possible to remove most of the coloring matters and waxes present in the films and around the seeds: in fact, the waxes are deposited by cooling from the alcoholic extract while the latter is very strongly colored.

On traite les graines lavées et essorées avec un antioxydant de manière à protéger leur huile de l'oxydation au cours des étapes ultérieures. Comme antioxydants, on peut citer les solutions aqueuses diluées d'acide ascorbique ou benzoi- que ou de leurs sels de sodium ou de potassium, par exemple une solution aqueuse contenant 30 à 50 ppm (partie par million) en poids d'acide ascorbique, à raison de 7-8% du poids des graines mises en oeuvre.The washed and drained seeds are treated with an antioxidant so as to protect their oil from oxidation during the subsequent stages. As antioxidants, there may be mentioned dilute aqueous solutions of ascorbic or benzolic acid or their sodium or potassium salts, for example an aqueous solution containing 30 to 50 ppm (parts per million) by weight of ascorbic acid, at a rate of 7-8% of the weight of the seeds used.

On presse les graines protégées p. ex. au moyen d'une presse à vis continue sous forte pression et on obtient jusqu'à 90% de l'huile contenue dans les graines selon le type de presse utilisée, les conditions de pressage et le nombre de cycles de pressage appliqués.The protected seeds are pressed p. ex. by means of a continuous screw press under high pressure and up to 90% of the oil contained in the seeds is obtained according to the type of press used, the pressing conditions and the number of pressing cycles applied.

On fait suivre lé pressage par une extraction par solvants du gâteau de pressage. On procèce au floconage sur cylindre aplatisseur des graines protégées et séchées. Cette mise en forme évite le colmatage et facilite l'extraction ultérieure de l'huile en donnant au produit la porosité permettant une bonne pénétration du solvant, et les flocons en particulier résistent à d'écrasement. On chauffe les flocons à 80-90 °C et on les presse sous une pression de 490-785 b (500-800 kg/cm2), en maintenant la température de la tête de la presse à une valeur inférieure à 90 °C. De cette manière, on obtient 50 à 60% de l'huile contenue dans les graines. Le gâteau de pressage a une densité de 0,58 à 0,65, soit environ le double de la densité des flocons et peut être convenablement percolé par le solvant d'extraction. On moud le gâteau de pressage et on procède à l'extraction du résidu moulu.The pressing is followed by solvent extraction from the pressing cake. Protected and dried seeds are flaked on a flattening cylinder. This shaping avoids clogging and facilitates the subsequent extraction of the oil by giving the product porosity allowing good penetration of the solvent, and the flakes in particular resist crushing. The flakes are heated to 80-90 ° C and pressed under a pressure of 490-785 b (500-800 kg / cm 2 ), maintaining the temperature of the press head at a value below 90 ° C . In this way, 50 to 60% of the oil contained in the seeds is obtained. The pressing cake has a density of 0.58 to 0.65, about twice the density of the flakes and can be appropriately percolated with the extraction solvent. The pressing cake is ground and the ground residue is extracted.

Dans cette étape, on extrait l'huile résiduelle avec un solvant non polaire, p. ex. de l'hexane à raison de 200 à 250% en poids d'hexane par rapport au résidu. On peut en variante utiliser le dioxyde de carbone liquide ou de préférence supercritique également dans cette étape, dans des conditions où il est faiblement polaire, p. ex. à 200-300 bar et 40-60 °C. On peut bien entendu utiliser p. ex. le dioxyde de carbone supercritique dans l'étape de lavage et dans l'étape d'extraction subséquente ou dans une seule de ces étapes, l'autre étant conduite avec p. ex. l'éthanol, respectivement l'hexane.In this step, the residual oil is extracted with a non-polar solvent, e.g. ex. hexane in an amount of 200 to 250% by weight of hexane relative to the residue. Alternatively, liquid carbon dioxide or preferably supercritical carbon dioxide can also be used in this step, under conditions where it is weakly polar, e.g. ex. at 200-300 bar and 40-60 ° C. One can of course use p. ex. supercritical carbon dioxide in the washing step and in the subsequent extraction step or in only one of these steps, the other being carried out with p. ex. ethanol, respectively hexane.

On réunit l'huile de pression et la solution d'extraction. On peut, bien que ces mesures constituent uniquement des options préférées, neutraliser le mélange pour supprimer les acides gras libres résiduels, éventuellement après en avoir évaporé partiellement le solvant, p. ex. dans le cas de l'hexane de sorte que la solution contienne environ 10% en poids d'huile, par l'hydroxyde de sodium ou de potassium concentré (2N), la refroidir à environ 0-4 °C pendant environ 24 heures et la filtrer à cette température de manière à en éliminer totalement les cires résiduelles. De même, la décoloration et la désodorisation ci-après constituent des options préférées: on décolore la solution par un adsorbant p. ex. le charbon activé ou les terres décolorantes activées à base de silicate d'aluminium activé comme la montmorillonite ou la bentonite à raison de 2-8% en poids par rapport à l'huile engagée à 20-60 °C puis on évapore le solvant. On désodorise ensuite l'huile par entrainement à la vapeur à 140-220 °C et de préférence à environ 180 °C sous un vide égal ou inférieur à 0,75 mb (1 torr).The pressure oil and the extraction solution are combined. It is possible, although these measures constitute only preferred options, to neutralize the mixture in order to remove the residual free fatty acids, possibly after having partially evaporated the solvent, p. ex. in the case of hexane so that the solution contains approximately 10% by weight of oil, by concentrated sodium or potassium hydroxide (2N), cool it to approximately 0-4 ° C for approximately 24 hours and filter it at this temperature so as to completely eliminate the residual waxes. Likewise, the following discoloration and deodorization are preferred options: lore the solution with an adsorbent p. ex. activated charcoal or activated bleaching earths based on activated aluminum silicate such as montmorillonite or bentonite at a rate of 2-8% by weight relative to the oil used at 20-60 ° C. and then the solvent is evaporated. The oil is then deodorized by steam entrainment at 140-220 ° C and preferably at approximately 180 ° C under a vacuum of 0.75 mb (1 torr) or less.

Selon une variante de préparation de l'huile, on ne procède pas au lavage préalable des graines (étape a)) mais on procède au pressage directement suivi éventuellement d'une extraction par un solvant du gâteau de pressage. Dans ce cas, la neutralisation, l'élimination des cires par décantation, la décoloration et la désodorisation comme indiquées ci-dessus (étapes f) à i)) sont indispensables à l'obtention d'une huile raffinée jaune pâle.According to a variant of preparation of the oil, the seeds are not washed beforehand (step a)) but the pressing is carried out directly followed optionally by extraction with a solvent from the pressing cake. In this case, neutralization, elimination of waxes by decantation, discoloration and deodorization as indicated above (steps f) to i)) are essential for obtaining a pale yellow refined oil.

Dans certains cas, on désire enrichir le corps gras en acide gamma-linolénique. Pour ce faire on saponifie l'huile débarrassée des cires et des acides gras libres par un hydroxyde alcalin, par exemple l'hydroxyde de potassium en milieu mé- thanol/eau à la concentration d'environ 11 %, on acidifie les sels obtenus par un acide minéral, p. ex. l'acide sulfurique 2N, on extrait les acides gras libérés par l'hexane, on sépare la phase organique et on la sèche p. ex. par addition de sulfate de sodium. On fractionne la phase organique par chromatographie haute performance en phase liquide, par passage sur colonnes de gel de silice chargées avec du nitrate d'argent et élution de préférence avec un mélange de dichlorométhane, toluène et éther diéthyHque 70/25/5 - 63/30/5 en mode isocratique, c'est-à-dire avec recyclage du mélange solvant de composition fixe et on obtient ainsi une fraction contenant environ 60% en poids d'acide gamma-linolénique et environ 40% d'acide alpha-linolénique.In some cases, it is desired to enrich the fatty substance with gamma-linolenic acid. To do this, the oil freed from waxes and free fatty acids is saponified with an alkali hydroxide, for example potassium hydroxide in methanol / water at a concentration of approximately 11%, the salts obtained are acidified. a mineral acid, e.g. ex. 2N sulfuric acid, the fatty acids liberated by hexane are extracted, the organic phase is separated and dried p. ex. by addition of sodium sulfate. The organic phase is fractionated by high performance liquid chromatography, by passage over columns of silica gel loaded with silver nitrate and elution preferably with a mixture of dichloromethane, toluene and diethyl ether 70/25/5 - 63 / 30/5 in isocratic mode, that is to say with recycling of the solvent mixture of fixed composition and a fraction containing approximately 60% by weight of gamma-linolenic acid and approximately 40% of alpha-linolenic acid is thus obtained. .

On peut isoler l'acide gamma-linolénique pratiquement pur en effectuant une chromatographie en phase liquide à haute performance avec support côté en C8 ou C18 en phase inversée avec gradient de mélange solvant acétonitrile/eau, mé- thanol/eau ou isopropanol/eau.Almost pure gamma-linolenic acid can be isolated by performing high performance liquid chromatography with support on the C 8 or C 18 side in reverse phase with gradient of solvent mixture acetonitrile / water, methanol / water or isopropanol / water.

Les corps gras obtenus selon l'invention peuvent être incorporés dans des compositions nutritives selon la demande de brevet européenne No. 92085. L'exemple suivant illustre l'invention. Dans celui-ci les parties et pourcentages sont exprimés en valeur pondérale sauf indication contraire.The fatty substances obtained according to the invention can be incorporated into nutritive compositions according to European patent application No. 92085. The following example illustrates the invention. In it the parts and percentages are expressed in weight value unless otherwise indicated.

ExempleExample

On moud 432 kg de pulpe de cassis séchée provenant du pressage des jus dans un moulin à disques et on tamise le produit moulu de manière à obtenir 261 kg de particules comprises entre 1 et 1,5 mm. On l'envoie dans un élutriateur et on receuille 214 kg d'une fraction lourde constituée essentiellement de graines. On lave 2 fois avec chaque fois 520 kg d'éthanol au reflux.432 kg of dried blackcurrant pulp are milled from the pressing of the juices in a disc mill and the ground product is sieved so as to obtain 261 kg of particles between 1 and 1.5 mm. We send it to an elutriator and we collect 214 kg of a heavy fraction consisting essentially of seeds. Wash twice with 520 kg of ethanol at reflux each time.

On pulvérise 14-16 d'eau contenant 30-50 ppm (parties par million) d'acide ascorbique sur les graines lavées précédement. On sèche les graines traitées à 70 °C pendant 30-40 min et on les met sous forme de flocons à l'aide d'un broyeur à cylindres aplatisseur. On chauffe les flocons à 80-90 °C pendant 30-40 min. Ceux-ci ont une densité de 0,35.The previously washed seeds are sprayed with 14-16 water containing 30-50 ppm (parts per million) of ascorbic acid. The treated seeds are dried at 70 ° C for 30-40 min and put into the form of flakes using a flattening roller mill. The flakes are heated to 80-90 ° C for 30-40 min. These have a density of 0.35.

On presse les flocons pendant 30-50 min dans une presse à vis continue sous une pression de 500-800 kg/cm2 avec une vitesse de rotation de la vis de 10-20 tours/min en maintenant la température de tête de la presse à 80-90 °C. On obtient ainsi 26-31 kg d'huile (environ 50-60% de l'huile présente dans les graines). Le gâteau de pressage a une densité de 0,60 qui permet une percolation sans colmatage lors de l'étape ultérieure d'extraction. On le moud et on l'extrait par 2 fois 370-400kg d'hexane au reflux pendant 3 h. Puis on refroidit et on filtre. Après évaporation de l'hexane, on receuille ainsi 22 à 26 kg d'huile supplémentaires.The flakes are pressed for 30-50 min in a continuous screw press under a pressure of 500-800 kg / cm 2 with a screw rotation speed of 10-20 revolutions / min while maintaining the head temperature of the press at 80-90 ° C. 26-31 kg of oil are thus obtained (approximately 50-60% of the oil present in the seeds). The pressing cake has a density of 0.60 which allows percolation without clogging during the subsequent extraction step. It is ground and extracted with 2 times 370-400 kg of hexane at reflux for 3 h. Then cool and filter. After evaporation of the hexane, 22 to 26 kg of additional oil are thus collected.

Claims (10)

1. A process for preparation of a fatty substance from pips of fruits of the Ribes genus, characterized by the following steps:
a) washing the pips with a polar solvent or a supercritical fluid in a polar condition,
b) treating the pips with an antioxidant in order to protect the oil contained therein against oxidation,
c) forming the protected pips into flakes,
d) pressing the flakes and collecting the oil,
e) extracting the rest of the oil from the press cake with a non-polar solvent or a supercritical fluid in a slightly polar condition and the removing the solvent or the supercritical fluid.
2. A process as claimed in claim 1, characterized by the further following steps:
f) mixing the pressed oil with a solution containing the residual oil of step e) and then neutralizing the mixture in order to eliminate the residual free fatty acids therefrom,
g) cooling the neutralized mixture, letting it settle and filtering it,
h) decolorizing the filtrate with an adsorbent and then removing the solvent and,
i) desodorizing the oil.
3. A process claimed in claim 2, characterized by suppressing step a).
4. A process as claimed in any one of claims 1 to 3, characterized by obtaining the pips by drying the press cake of blackcurrant juices, by milling and sieving it in order to obtain particles of from 1 to 1.5 mm and by separating the pips by elutriation.
5. A process as claimed in claim 1 or 2, characterized by washing the pips with refluxing ethanol.
6. A process as claimed in any one of claims 1 to 3, characterized by pressing the flakes under a pressure of from 490 to 785 b (500-800 kg/cm2) while maintaining the temperature of the press head under 90 °C.
7. A process as claimed in any one of claims 1 to 3, characterized by extracting the press cake with refluxing hexane.
8. A process as claimed in claim 2 or 3, characterized by partially evaporating the non-polar solvent in step
f) to obtain a solution containing 80 to 90% by weight of solvent, neutralizing the solution with a concentrated alkali and by maintaining the solution in step g) at a temperature of 0 °C to 4 °C during about 24 h and filtering it.
9. A process as claimed in claim 2 or 3, characterized by decolorizing the filtrate in step h) with from 2 to 8% of activated adsorbent based on the weight of the fatty substance in solution.
10. A process as claimed in claim 2 or 3, characterized by desodorizing the oil in step i) at a temperature of from 140 °C to 220 °C under a vacuum under 0.75 mb (1 torr).
EP83110241A 1983-10-14 1983-10-14 Process for the preparation of fatty material Expired EP0137862B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE8383110241T DE3373673D1 (en) 1983-10-14 1983-10-14 Process for the preparation of fatty material
AT83110241T ATE29733T1 (en) 1983-10-14 1983-10-14 PROCESS FOR THE MANUFACTURE OF FAT.
EP83110241A EP0137862B1 (en) 1983-10-14 1983-10-14 Process for the preparation of fatty material
ES536678A ES536678A0 (en) 1983-10-14 1984-10-11 PROCEDURE FOR THE PREPARATION OF FATS FROM FRUIT PEPITES OF THE GENUS RIBES.
DK487084A DK169557B1 (en) 1983-10-14 1984-10-11 Process for the production of fats
JP59214026A JPS60104195A (en) 1983-10-14 1984-10-12 Manufacture of fatty substance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83110241A EP0137862B1 (en) 1983-10-14 1983-10-14 Process for the preparation of fatty material

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EP0137862A1 EP0137862A1 (en) 1985-04-24
EP0137862B1 true EP0137862B1 (en) 1987-09-16

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JPH0195196A (en) * 1987-10-07 1989-04-13 Sumitomo Heavy Ind Ltd Method of extracting oleaginous components from seed of plant
JPH02235996A (en) * 1989-03-09 1990-09-18 T Hasegawa Co Ltd Technique for extraction of vegetable oil
JPH02235995A (en) * 1989-03-09 1990-09-18 T Hasegawa Co Ltd Technique for extraction of vegetable oil

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FR2197605A1 (en) * 1972-09-06 1974-03-29 Williams John Foodstuff or skin nutrient to combat cholesterolaemia - contains arachidonic acid or gamma linolenic acid or esters and salts thereof
FR2255055A1 (en) * 1973-12-19 1975-07-18 Pourrat Henri Raspberry seed oil compsns - with antiinflammatory activity, for cosmetic and pharmaceutical use

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JPH0153998B2 (en) 1989-11-16
DK487084D0 (en) 1984-10-11
ATE29733T1 (en) 1987-10-15
DK487084A (en) 1985-04-15
ES8603557A1 (en) 1986-01-01
EP0137862A1 (en) 1985-04-24
DK169557B1 (en) 1994-11-28
ES536678A0 (en) 1986-01-01
DE3373673D1 (en) 1987-10-22
JPS60104195A (en) 1985-06-08

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