EP0035298B1 - Verfahren zur Lösungsmittelfraktionierung von Olivenöl-Stearin und verwandte Produkte - Google Patents

Verfahren zur Lösungsmittelfraktionierung von Olivenöl-Stearin und verwandte Produkte Download PDF

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Publication number
EP0035298B1
EP0035298B1 EP81200180A EP81200180A EP0035298B1 EP 0035298 B1 EP0035298 B1 EP 0035298B1 EP 81200180 A EP81200180 A EP 81200180A EP 81200180 A EP81200180 A EP 81200180A EP 0035298 B1 EP0035298 B1 EP 0035298B1
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EP
European Patent Office
Prior art keywords
precipitate
fraction
solvent
solution
stearine
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Expired
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EP81200180A
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English (en)
French (fr)
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EP0035298A1 (de
Inventor
Francis E. Luddy
Sergio Longhi
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Societe des Produits Nestle SA
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Societe des Produits Nestle SA
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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
    • C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • C11B7/0008—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents

Definitions

  • the present invention relates to a process for the solvent fractionation of olive oil stearine and to the related products.
  • Olive oil stearine a high melting fatty material, is a by-product of the edible oil industry.
  • Solvent fractionation of fats is a thermomechanical crystallization and separation process. It is known from FR-A-2,427,386 that a cocoa butter substitute can be made by a complex multistep process requiring three fractionation steps and one chemical modification step. Also from US-A-3,431,116 it is known that a cocoa butter substitute can be made by a single stage solvent fractionation of cottonseed oil stearine. GB-A-750.045 generally teaches the use of any common organic solvent from which the fatty substances may be crystallized without alteration of their normal state.
  • the object of the invention is the taking of this economically unattractive fatty material and by virtue of expertise of Applicants in oil and fat technology create new, useful and more valuable fatty products by two simple fractionation schemes to produce said useful products from olive oil stearine, the disclosed process requiring the modest temperature of +15°C in the one-step process and of +25°C in the first step and +2°C in the second step of the two-step process.
  • glycerides are largely disaturated monounsaturated glycerides of palmitic, stearic and oleic acids together with lesser amounts of diunsaturated monosaturated glycerides, and triunsaturated glycerides of the same fatty acids.
  • cocoa butter is a very complex mixture of glycerides and it is not unreasonable that olive stearine which contains the same fatty acids and many of the same glycerides might be fractionated to yield a fraction whose glycerides have melting properties similar to cocoa butter.
  • Olive oil stearine according to its DSC (Differential Scanning Calorimetry) melting profile of Figure 1 has a melting range from 55°-70°C so it obviously contains some very high melting glycerides. Consequently, according to the present invention, the solvent fractionation process is carried out to remove a substantial amount of these high melting glycerides leaving behind a fraction of mixed glycerides of more appropriate lower melting properties.
  • the processes of this invention may be carried out by either the "batch” or “continuous” fraction process or combination of these but only the "batch” process will be cited in the examples.
  • the fatty acid composition of a typical olive oil stearine is given in the following table: while the thermal properties of the stearine are graphically depicted by the Differential Scanning Calorimetry (DSC) profile in Figure 1.
  • DSC Differential Scanning Calorimetry
  • the stearine is not a brittle solid but is high melting which indicates a preponderance of high melting glycerides mixed with many lower melting glycerides. It is obvious that fatty materials of this type lend themselves to solvent crystallization processes for the production of fractions with specific physical properties.
  • the olive oil stearine is melted and dissolved in hot'solvent. If hydrocarbon solvent is used, the mixture with boiling range of about 70°C is preferred especially for ease of solvent recovery.
  • the solvent fat mixture is warmed to about 60°C to insure complete solution. It is then allowed to cool to the crystallization temperature with or without stirring. Cooling of the mixture can be effected in any of several ways.
  • the crystallizer may be equipped with appropriate cooling coils or the crystallizer might be held in a thermostated room.
  • the precipitate may be collected by either vacuum or pressure filtering or by centrifugation or by decantation or by a combination of these techniques.
  • the collected precipitates should be washed with fresh solvent at least 2°C cooler than the crystallization temperature. Efficient washing of the precipitate will produce sharply defined fractions as well help to maximise the yield.
  • the fractionation may also be carried out in a much shorter time interval in a continuous system by utilizing high speed, scraped-surface crystallizers.
  • the number of the crystallization steps will depend on the nature and number of desired fractions.
  • Figure 2 shows the DSC melting profile of the high melting solid fat (1-P-1) while Figure 3 gives the DSC melting profile for the softer, semisolid fat (1-F-1).
  • the soft, semisolid glyceride fractions thus isolated were found to be compatible with cocoa butter since when mixed with cocoa butter they did not distort the original melting characteristics of cocoa butter.
  • the DSC melting profile for pure cocoa butter is shown in Figure 7, and for comparison the DSC melting profiles of the mixture of 85% cocoa butter and 15% olive oil stearine confectionery fat (1-F-1) and (2-P-2) are presented in Figure 8 and 9.
  • the DSC melting profiles of the mixtures show little distortion of the characteristics shown by the pure cocoa butter.
  • the olive oil confectionery fat has also been mixed in standard dark chocolate formulations at the 15% level of total fat and the resultant products found to have excellent properties, equal to chocolate containing only pure cocoa butter.
  • fraction 1-F-1 and fraction 2-P-2 may be mixed with cocoa butter to yield confectionery fats of melting range which approximates the melting range of pure cocoa butter.
  • the Applicants data indicate that mixtures containing a minimum of 1 % of fraction 1-F-1 or 2-P-2 and 99% of cocoa butter or a maximum of 99% of fraction 1-F-1 or 2-P-2 will produce suitable fatty mixtures. Since these fractions melt slightly above body temperature, they are suitable materials for cosmetic or pharmaceutical bases.
  • Fraction 2-F-2 Figure 6
  • the high melting fractions, 1-P-1 and 2-P-1 could be used as a cosmetic or pharmaceutical base, or they may be subjected to chemical or enzymatic hydrolysis and used as source of palmitic or stearic acid.
  • Fraction 2-F-2, Figure 6 comprises the liquid portion of olive oil stearine.
  • the liquid portion or fraction of the olive oil stearine is also a source for the unsaturated hydrocarbon squalene, a material of commercial interest, and a source of oleic acid after chemical or enzymatic hydrolysis.
  • Example 1 will illustrate a process with the maximum yield of a confectionery fat fraction while Example 2 will illustrate a process with maximum yield of the oil fraction.
  • the precipitate is collected by filtering under vacuum or pressure.
  • the collected precipitate and filtrate are individually processed in conventional evaporators and deodorizers and the hydrocarbon solvent is recovered at the same time.
  • the yield of the high melt solid fraction is 300 grams or 30% and the melting characteristics of this material are shown by the DSC melting profiles in Figure 2.
  • the yield of the softer, lower melting confectionery fat fraction is 700 grams or 70%.
  • the melting characteristics of the confectionery fat fraction (1-F-1) are illustrated by the DSC melting profile of Figure 3.
  • the precipitate (2-P-1) is collected and washed with fresh acetone previously cooled to about 23°C and equal to about 10% of the original crystallization volume. This solvent wash is added to the filtrate (2-F-1) prior to the next crystallization step.
  • the combined filtrates are returned to the crystallizer, the solvent ratio is adjusted to a ratio of 3 liters of acetone per kilo of filtrate.
  • the solution is allowed to cool with stirring until the final crystallization temperature of 2°C is reached.
  • the crystalline precipitate is collected and washed at one or more times with a volume of fresh acetone at 0°C equal to about 10% of the original crystallization volume.
  • the collected precipitate and filtrate are processed individually by conventional evaporators and deodorizers.
  • the yield of the high melt fraction (2-P-1) is 350 grams or 35%
  • the yield of the softer, semisolid fraction (2-P-2) is 200 grams or 20%
  • the yield of the remaining material is the oil fraction (2-F-2) is 450 grams or 45%.
  • the thermal characteristics of the fractions as defined by Differential Scanning Calorimetry are shown in Figure 4, for the high melt fraction (2-P-1), Figure 5 for the softer semisolid fraction (2-P-2), and Figure 6 for the oil fraction (2-F-2).
  • the fatty acid compositions of the fractions are given in Table (C) above.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)

Claims (14)

1. Einstufiges Verfahren zur Lösungsmittelfraktionierung von Olivenölstearin, bestehend aus dem
a) Auflösen des Stearins in einem Kohlenwasserstofflösungsmittel eines Siedebereichs unter 130°C, wobei das Lösungsmittelverhältnis 5 bis 1 ist und die Mischung auf eine ausreichend hohe Temperatur zur Sicherstellung einer Lösung erhitzt ist;
b) Kristallisieren der Lösung durch langsames Abkühlen auf 15°C;
c) Halten der Lösung auf dieser Temperatur, bis das Kristallisationsgleichgewicht erreicht ist;
d) Abtrennen der Lösung von der Ausfällung durch Vakuum- oder Druckfiltration, Dekantieren oder Zentrifugieren, Einsammeln und Behandeln der Ausfällung und des Filtrats, wobei die Ausfällung eine hochschmelzende, feste Fettfraktion, 1-P-1, in einer 30 %igen Ausbeute und das Filtrat, 1-F-1, eine weichere, halbfeste Fettfraktion in einer 70 %igen Ausbeute zur Verwendung als Konfektfett ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Lösungsmittel eine Mischung von Kohlenwasserstoffen mit einem Siedepunkt von etwa 70°C ist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein Rühren durchgeführt wird.
4. Zweistufiges Verfahren zur Lösungsmittelfraktionierung von Olivenölstearin, bestehend aus dem
a) Auflösen des Stearins in einem Acetonlösungsmittel, wobei das Lösungsmittelverhältnis, 7,5 bis 1 ist, und Erhitzen der Mischung auf eine Temperatur, die ausreichend hoch ist, um eine vollständige Lösung sicherzustellen;
b) Kristallisieren der Lösung durch langsames Kühlen auf 25°C;
c) Halten dieser Lösung auf der genannten Temperatur, bis das Kristallisationsgleichgewicht erreicht ist;
d) Abtrennen der Lösung von der Ausfällung durch Vakuum- oder Druckfiltration, Dekantieren oder Zentrifugieren und Einsammeln der ersten Ausfällung (2-P-1), wobei diese Ausfällung ein hochschmelzendes, festes Fett in 35 %iger Ausbeute ist;
e) Waschen der zuerst gesammelten Ausfällung mit frischem Acetonlösungsmittel, das auf eine Temperatur abgekühlt ist, die niedriger als die Kristallisationstemperatur der ersten Kristallisation ist;
f) Zugabe der Lösungsmittelwaschflüssigkeit der Phase (e) zu dem ersten Filtrat (2-F-1);
g) Kristallisieren der kombinierten Filtrate der Phase (f) mit einem auf 3 bis 1 eingestellten Lösungsmittelverhältnis durch langsames Kühlen auf 2°C
h) Einsammeln der zweiten Ausfällung (2-P-2) in der gleichen Weise wie bei der ersten Ausfällung und mindestens einmaliges Waschen mit einem Volumen frischen Acetons bei 0°C, das etwa 10% des ursprünglichen Volumens ausmacht; und
i) einzelnes Behandeln der Ausfällung der Phase (h) und des Filtrats der Phase (h), wobei die zweite Ausfällung (2-P-2) eine weichere halbfeste Fraktion in einer 20 %igen Ausbeute und das zweite Filtrat (2-F-2) eine klare Ölfraktion in einer 45 %igen Ausbeute ist.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß ein Rühren durchgeführt wird.
6. Eine hochschmelzende Glyzerid-Fraktion eines Schmelzpunkts von 60 bis 70°C, erhalten nach den Verfahren gemäß den Ansprüchen 1 bis 5.
7. Eine halbfeste Glyzerid-Fraktion eines Schmelzpunktes unter 46°C, erhalten nach dem Verfahren gemäß den Ansprüchen 1 bis 5.
8. Eine Ölfraktion mit einem Stockpunkt unter 10°C, erhalten nach dem Verfahren gemäß den Ansprüchen 4 und 5.
9. Ein Konfektfett mit einem Gehalt an 1 bis 99% der Fettfraktion der Ansprüche 1 bis 5, (1-F-1) und (2-P-2), und 99 bis 1% Kakaobutter und an irgendeinem anderen ähnlichen Konfektfett.
10. Fettausgangsmaterial für Kosmetika und Pharmazeutika, enthaltend die hochschmelzenden Glyzeride gemäß Anspruch 6.
11. Ausgangsmaterial für Kosmetika und Pharmazeutika, enthaltend das halbfeste Glyzeridmaterial gemäß Anspruch 7.
12. Ausgangsstoff von Palmitin- und Stearinsäuren, erhalten durch chemische oder enzymatische Hydrolyse der hochschmelzenden Glyzerid-Fraktion gemäß den Ansprüchen 6 und 7.
13. Ausgangsstoff der Ölsäure, erhalten durch die chemische oder enzymatische Hydrolyse der niedrigschmelzenden Glyzerid-Fraktion gemäß Anspruch 8.
14. Ausgangsstoff des ungesättigten Kohlenwasserstoffsqualens, isoliert aus der niedrigschmelzenden Glyzerid-Fraktion gemäß Anspruch 8.
EP81200180A 1980-02-28 1981-02-16 Verfahren zur Lösungsmittelfraktionierung von Olivenöl-Stearin und verwandte Produkte Expired EP0035298B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2022580 1980-02-28
IT20225/80A IT1141251B (it) 1980-02-28 1980-02-28 Processo per il frazionamento in solvente di stearina dell'olio d'oliva e relativi prodotti

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EP0035298A1 EP0035298A1 (de) 1981-09-09
EP0035298B1 true EP0035298B1 (de) 1985-07-24

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EP81200180A Expired EP0035298B1 (de) 1980-02-28 1981-02-16 Verfahren zur Lösungsmittelfraktionierung von Olivenöl-Stearin und verwandte Produkte

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EP (1) EP0035298B1 (de)
DE (1) DE3171441D1 (de)
IT (1) IT1141251B (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1140338B (it) * 1981-12-15 1986-09-24 Biocell Spa Procedimento per il frazionamento in solvente di stearine di olio di palma ed impiego dei prodotti relativi
ES2168997B1 (es) * 2000-11-07 2003-06-16 Aceites Borges Pont S A Procedimiento para la elaboracion de pasta de aceite de oliva.
MXPA05001630A (es) 2002-08-12 2005-04-25 Unilever Nv Grasa de trigliceridos.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB750045A (en) * 1953-03-13 1956-06-06 Texaco Development Corp Improvements in or relating to the treatment of a mixture of saturated, mono-unsaturated and poly-unsaturated fatty acid compounds
US3431116A (en) * 1965-08-05 1969-03-04 Us Agriculture Process for the production of confectionery fats
FR2427386A1 (fr) * 1978-05-31 1979-12-28 Lesieur Cotelle Procede pour la production de plusieurs fractions comestibles a partir de corps gras naturels et fractions ainsi obtenues

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IT8020225A0 (it) 1980-02-28
IT1141251B (it) 1986-10-01
DE3171441D1 (en) 1985-08-29
EP0035298A1 (de) 1981-09-09

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