EP0137862A1 - Verfahren zur Herstellung von Fettstoffen - Google Patents

Verfahren zur Herstellung von Fettstoffen Download PDF

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Publication number
EP0137862A1
EP0137862A1 EP83110241A EP83110241A EP0137862A1 EP 0137862 A1 EP0137862 A1 EP 0137862A1 EP 83110241 A EP83110241 A EP 83110241A EP 83110241 A EP83110241 A EP 83110241A EP 0137862 A1 EP0137862 A1 EP 0137862A1
Authority
EP
European Patent Office
Prior art keywords
solvent
seeds
oil
weight
polar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP83110241A
Other languages
English (en)
French (fr)
Other versions
EP0137862B1 (de
Inventor
Helmut Traitler
Heike Winter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe des Produits Nestle SA
Nestle SA
Original Assignee
Societe des Produits Nestle SA
Nestle SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe des Produits Nestle SA, Nestle SA filed Critical Societe des Produits Nestle SA
Priority to AT83110241T priority Critical patent/ATE29733T1/de
Priority to EP83110241A priority patent/EP0137862B1/de
Priority to DE8383110241T priority patent/DE3373673D1/de
Priority to DK487084A priority patent/DK169557B1/da
Priority to ES536678A priority patent/ES8603557A1/es
Priority to JP59214026A priority patent/JPS60104195A/ja
Publication of EP0137862A1 publication Critical patent/EP0137862A1/de
Application granted granted Critical
Publication of EP0137862B1 publication Critical patent/EP0137862B1/de
Expired legal-status Critical Current

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Classifications

    • 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-eicosatetraene), which is even 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 ⁇ arachidonic acid) and may even be nonexistent (eg for cats ) if the enzyme A-6-desaturase is absent or inactivated.
  • 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, hepatic disorder joint, neurological and mental).
  • biochemical disorders or to organic lesions e.g. coagulation disorders, dermatological lesions, endocrine disorders, myocardial damage, hepatic disorder joint, neurological and mental.
  • French patent No. 2,255,055 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 an appreciable percentage, at least 4% by weight of acid. gamma-linolenic.
  • 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 until now 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
  • the blackcurrant oil which is preferred because of its high content of gamma-linolenic acid, also contains from 1 to 2% by weight of body 'unsaponifiables, such as aliphatic alcohols, hydrocarbons, tocopherols, squalene, S-sitosterol, campesterol and A-7 stigmasterol. Its density is 0.9215 g / cm 3 (at 20 ° C) and its viscosity 28.3 centipoise (at 20 ° C).
  • the invention relates to a process for preparing fatty substances from fruit seeds of the genus Ribes, characterized in that a vegetable material containing these seeds is pressed so as to obtain a fatty substance containing at least 4% by weight of gamma-linolenic acid practically devoid of the odorous compounds, free fatty acids, colorings and waxes of these fruits.
  • 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, eg. 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 weight yield 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 about 2 hours and a second time for about 30 - 60 minutes, or continuously for about 2 hours and then the residue is wrung.
  • the seeds can be washed using p. ex. carbon dioxide at 250-350 bar and 60-80 ° C in 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 cakes are treated enzymatically, p. ex. with an aqueous solution containing 0.01 to 0.5% by weight of cellulase at pH 4-5 at a temperature of 38-42 ° C for 1 to 4 h. or at room temperature for 12 to 15 h.
  • the seeds can thus be easily separated from the porridge and at the same time at least partially freed from waxes and coloring matters.
  • the washed and wrung out 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 benzoic 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 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 extraction by solvents from the pressing cake.
  • the 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 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 adequately percolated by 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: the solution is discolored 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 about 180 ° C under a vacuum equal to or less than 1 torr.
  • the seeds are not washed beforehand 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 are essential for obtaining a pale yellow refined oil.
  • we want to enrich the fatty substance with gamma-linolenic acid we saponify the oil, free of waxes and free fatty acids, by an alkaline hydroxide, for example potassium hydroxide in methanol / water. at the concentration of approximately 11%, the salts obtained are acidified with a mineral acid, p. 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.
  • an alkaline hydroxide for example potassium hydroxide in methanol / water.
  • the organic phase is fractionated by high pressure 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 - 65/30/5 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% alpha-linolenic acid.
  • Almost pure gamma-linolenic acid can be isolated by performing high-pressure liquid phase chromatography with support rated C a or C 18 in reverse phase with solvent mixture gradient acetonitrile / water, methanol / water or isopropanol / water.
  • the fatty substances obtained according to the invention can be incorporated into nutritional 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 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. 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 cooled and filtered. After evaporation of the hexane, 22 to 26 kg of additional oil are thus collected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Fats And Perfumes (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Preparation Of Fruits And Vegetables (AREA)
EP83110241A 1983-10-14 1983-10-14 Verfahren zur Herstellung von Fettstoffen Expired EP0137862B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT83110241T ATE29733T1 (de) 1983-10-14 1983-10-14 Verfahren zur herstellung von fettstoffen.
EP83110241A EP0137862B1 (de) 1983-10-14 1983-10-14 Verfahren zur Herstellung von Fettstoffen
DE8383110241T DE3373673D1 (en) 1983-10-14 1983-10-14 Process for the preparation of fatty material
DK487084A DK169557B1 (da) 1983-10-14 1984-10-11 Fremgangsmåde til fremstilling af fedtstoffer
ES536678A ES8603557A1 (es) 1983-10-14 1984-10-11 Procedimiento para la preparacion de grasas a partir de pepitas de frutos del genero ribes.
JP59214026A JPS60104195A (ja) 1983-10-14 1984-10-12 脂肪性物質の製造法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83110241A EP0137862B1 (de) 1983-10-14 1983-10-14 Verfahren zur Herstellung von Fettstoffen

Publications (2)

Publication Number Publication Date
EP0137862A1 true EP0137862A1 (de) 1985-04-24
EP0137862B1 EP0137862B1 (de) 1987-09-16

Family

ID=8190746

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83110241A Expired EP0137862B1 (de) 1983-10-14 1983-10-14 Verfahren zur Herstellung von Fettstoffen

Country Status (6)

Country Link
EP (1) EP0137862B1 (de)
JP (1) JPS60104195A (de)
AT (1) ATE29733T1 (de)
DE (1) DE3373673D1 (de)
DK (1) DK169557B1 (de)
ES (1) ES8603557A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0195196A (ja) * 1987-10-07 1989-04-13 Sumitomo Heavy Ind Ltd 植物の種子から油性成分を抽出する方法
JPH02235996A (ja) * 1989-03-09 1990-09-18 T Hasegawa Co Ltd 植物油の抽出方法
JPH02235995A (ja) * 1989-03-09 1990-09-18 T Hasegawa Co Ltd 植物油の抽出法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
ES536678A0 (es) 1986-01-01
ES8603557A1 (es) 1986-01-01
DK487084D0 (da) 1984-10-11
ATE29733T1 (de) 1987-10-15
JPH0153998B2 (de) 1989-11-16
EP0137862B1 (de) 1987-09-16
DK169557B1 (da) 1994-11-28
DE3373673D1 (en) 1987-10-22
DK487084A (da) 1985-04-15
JPS60104195A (ja) 1985-06-08

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