EP0591981B1 - Process for the extraction of fats and oils - Google Patents

Process for the extraction of fats and oils Download PDF

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Publication number
EP0591981B1
EP0591981B1 EP93116266A EP93116266A EP0591981B1 EP 0591981 B1 EP0591981 B1 EP 0591981B1 EP 93116266 A EP93116266 A EP 93116266A EP 93116266 A EP93116266 A EP 93116266A EP 0591981 B1 EP0591981 B1 EP 0591981B1
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Prior art keywords
extraction
oils
oil
fats
pressure
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EP93116266A
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German (de)
French (fr)
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EP0591981A1 (en
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Jürgen Dr. Heidlas
Jan Dr. Cully
Heinz-Rüdiger Dr. Vollbrecht
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Evonik Operations GmbH
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SKW Trostberg AG
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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
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C11B1/104—Production of fats or fatty oils from raw materials by extracting using super critical gases or vapours

Definitions

  • the present invention relates to a process for the extraction of fats and oils from natural substances, such as e.g. Vegetable, animal or microbial raw materials, with the help of liquid propane as a solvent, this process for the production of fats and oils as well as for the production of degreased or de-oiled products, which are becoming increasingly important as low-fat and thus low-calorie products in the food sector. is applicable.
  • natural substances such as e.g. Vegetable, animal or microbial raw materials
  • a disadvantage of conventional solvent extraction is the fact that most solvents are not toxicologically safe and that the extracted fats and oils and the extraction residues must be largely solvent-free before they can be used for food or feed purposes. This requires comparatively high temperatures, which can negatively affect the sensory properties of the products.
  • the separation For the degreasing of animal raw materials, such as fatty meat, the separation has the largest technical Meaning.
  • the difference in density of meat and fat components is usually used after thermal or mechanical digestion of the starting material in order to carry out a separation in separators or decanters.
  • this process cannot produce fatty meat products with a fat content lower than 10%, otherwise the loss of meat is too high.
  • extractive processes must be used, which have the disadvantages already mentioned in the case of the use of organic solvents.
  • the present invention was therefore based on the object of developing a process for the extraction of fats and oils from natural substances with the aid of propane as a solvent, which does not have the disadvantages of the prior art mentioned and which, without great technical outlay, has both sufficient gas loading with fats and oils as well as a good sensory quality of the products.
  • all fat-containing or oil-containing natural substances based on plants, animals or microbes can be used for the process according to the invention.
  • vegetable fats or oils are olive oil, palm oil, bamboo fat, coconut fat, cocoa butter, coffee oils, peanut butter, rapeseed oil (rapeseed oil), flax oil (linseed oil), sunflower oil, wheat germ oil, rice germ oil, cottonseed oil, corn germ oil, soybean oil, palm kernel oil and pumpkin seed oil.
  • beef or veal and marine oils such as e.g. Fish oils in question.
  • the method according to the invention can also be used for fermentation residues, for example from yeasts, fungi or bacteria.
  • the extraction material in comminuted, pelletized form.
  • the (in particular solid) starting material have a have a high water content, such as meat or fermentation residues, it has proven to be particularly advantageous to reduce the moisture to below 50% by suitable drying methods before the extraction.
  • the extraction with liquid propane is carried out in a very narrow and defined pressure and temperature range which is 10 to 30 bar or 10 to 55 ° C.
  • the process is preferably carried out at an extraction pressure of 15 to 25 bar and an extraction temperature of 20 to 45 ° C.
  • the extraction pressure and temperature must be coordinated so that the propane is in a liquid state.
  • the amount of propane gas used can be varied within wide limits and depends essentially on the amount of oil or fat to be extracted. Depending on the type of raw material, 2.5 to 500 g of liquid propane are normally required per g of fat or oil to be extracted. The maximum gas loading with lipid substances under these extraction conditions is 5 to 25% by weight, depending on the type of fat or oil extracted.
  • the purity of the propane gas used is relatively uncritical in most cases, i.e. noticeable amounts of impurities from homologous hydrocarbons (due to the refining process) can also be present without any noticeable loss in quality.
  • Propane is preferably used in technical purity of approx. 90% and in deodorized form.
  • the extraction with liquid propane can in some cases also be carried out in two or more stages in order to obtain the fats or oils completely.
  • the propane gas is preferably circulated in order to be able to load the desired lipid substances several times, but it is also possible to contact the extraction material only once with the extraction medium.
  • several extraction autoclaves can be connected in series and the extraction medium can be flowed through in succession.
  • the maximum achievable gas load of the liquid propane can always be optimally used by suitably switching the sequence of these autoclaves (e.g. flow through according to the advanced degree of extraction).
  • fats and oils dissolved in the liquid propane are separated by reducing the pressure and / or increasing the temperature, a reduction in pressure and an increase in temperature to 80 80 ° C. having proven particularly advantageous. In this way it is ensured that no undesired reactions such as isomerization of the double bonds of polyunsaturated fatty acids take place during the deposition.
  • the deposition is carried out by isobaric evaporation of the solvent, as a result of which the economy of the process can be increased significantly.

Abstract

A process for the extraction of fats and oils from natural substances with the aid of liquid propane as solvent is described and entails the extraction being carried out under a pressure of 10 to 30 bar and a temperature of 10 to 55 DEG C and the deposition of the extracted fats and oils from the solvent being carried out by reducing the pressure and/or increasing the temperature up to </= 80 DEG C. It is possible in this way to obtain high-quality products in good yield and under mild conditions.

Description

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Extraktion von Fetten und Ölen aus Naturstoffen, wie z.B. pflanzlichen, tierischen oder mikrobiellen Ausgangsmaterialien, mit Hilfe von flüssigem Propan als Lösemittel, wobei dieses Verfahren sowohl zur Gewinnung von Fetten und Ölen als auch zur Herstellung von entfetteten oder entölten Produkten, die als fett- und somit kalorienarme Produkte im Lebensmittelbereich zunehmend an Bedeutung gewinnen, anwendbar ist.The present invention relates to a process for the extraction of fats and oils from natural substances, such as e.g. Vegetable, animal or microbial raw materials, with the help of liquid propane as a solvent, this process for the production of fats and oils as well as for the production of degreased or de-oiled products, which are becoming increasingly important as low-fat and thus low-calorie products in the food sector. is applicable.

Prinzipiell stehen für die Entfettung und Entölung beispielsweise pflanzlicher Produkte zwei Verfahren zur Verfügung: die Extraktion und das Pressen. Das Pressen ist unter wirtschaftlichen Gesichtspunkten nur dann vorteilhaft, wenn der Fett- und Ölgehalt des Ausgangsmaterials relativ hoch (> 25 Gew.-%) ist. Es verbleibt hierbei jedoch auch unter optimaler Ausnutzung des Verfahrens im Preßrückstand ein Restfettgehalt von mindestens 4 bis 5 Gew.-%. Dagegen sind extraktive Verfahren mit normalen organischen Lösemitteln, wie z.B. Hexan oder Leichtbenzin, auch für Ausgangsprodukte mit einem niedrigen Fettgehalt geeignet, wobei der Restgehalt im Rückstand in der Regel auf unter 1 Gew.-% gesenkt werden kann. Nachteilig bei der herkömmlichen Lösemittelextraktion ist die Tatsache, daß die meisten Lösemittel toxikologisch nicht unbedenklich sind und daß die extrahierten Fette und Öle sowie die Extraktionsrückstände weitgehend lösemittelfrei sein müssen, bevor sie für Nahrungs- oder Futtermittelzwecke eingesetzt werden können. Hierfür sind vergleichsweise hohe Temperaturen erforderlich, welche die sensorischen Eigenschaften der Produkte negativ beeinflussen können.In principle, two processes are available for degreasing and de-oiling plant products, for example: extraction and pressing. From an economic point of view, pressing is only advantageous if the fat and oil content of the starting material is relatively high (> 25% by weight). However, even with optimal use of the process, a residual fat content of at least 4 to 5% by weight remains in the press residue. In contrast, extractive processes with normal organic solvents, e.g. Hexane or light petrol, also suitable for raw materials with a low fat content, whereby the residual content in the residue can usually be reduced to less than 1% by weight. A disadvantage of conventional solvent extraction is the fact that most solvents are not toxicologically safe and that the extracted fats and oils and the extraction residues must be largely solvent-free before they can be used for food or feed purposes. This requires comparatively high temperatures, which can negatively affect the sensory properties of the products.

Für die Entfettung von tierischem Ausgangsmaterial, wie z.B. fettem Fleisch, besitzt das Separieren die größte technische Bedeutung. Bei diesem Verfahren wird meist nach einem thermischen oder mechanischen Aufschluß des Eduktes der Dichteunterschied von Fleisch- und Fettbestandteilen ausgenutzt, um eine Trennung in Separatoren oder Dekantern durchzuführen. Aus wirtschaftlichen Gründen können mit diesem Verfahren keine Produkte aus fettem Fleisch hergestellt werden, deren Fettgehalt niedriger als 10 % ist, da sonst die Verluste an Fleisch zu hoch sind. Für die Herstellung von Fleischprodukten mit einem niedrigeren Fettgehalt müssen deshalb extraktive Verfahren eingesetzt werden, die im Falle der Verwendung von organischen Lösemitteln die bereits erwähnten Nachteile aufweisen.For the degreasing of animal raw materials, such as fatty meat, the separation has the largest technical Meaning. In this process, the difference in density of meat and fat components is usually used after thermal or mechanical digestion of the starting material in order to carry out a separation in separators or decanters. For economic reasons, this process cannot produce fatty meat products with a fat content lower than 10%, otherwise the loss of meat is too high. For the production of meat products with a lower fat content, therefore, extractive processes must be used, which have the disadvantages already mentioned in the case of the use of organic solvents.

Zur Umgehung dieses Problems wurde in den letzten Jahren die Extraktion mit verdichteten Gasen insbesondere für die Gewinnung von empfindlichen Naturstoffen eingeführt, wobei sich im technischen Bereich vor allem Kohlendioxid (CO2) als Extraktionsmedium durchgesetzt hat. Die Extraktion von Fetten und Ölen mit überkritischem CO2 ist wegen dessen geringen Lösevermögens erst in sehr hohen Druckbereichen (> 500 bar) befriedigend, was technisch aufwendig und folglich kostenintensiv ist und somit nur bei Produkten mit sehr hoher Wertschöpfung in Frage kommt. Dieser Nachteil kann auch durch den Zusatz von Schleppmitteln zu CO2 nur teilweise ausgeglichen werden, wobei der zusätzliche Regelaufwand für die Schleppmitteldosierung als weiterer Nachteil anzusehen ist.In order to circumvent this problem, extraction with compressed gases has been introduced in the past few years, in particular for the extraction of sensitive natural products, with carbon dioxide (CO 2 ) in particular having established itself as the extraction medium in the technical field. The extraction of fats and oils with supercritical CO 2 is only satisfactory due to its low solvency in very high pressure ranges (> 500 bar), which is technically complex and consequently cost-intensive and is therefore only suitable for products with very high added value. This disadvantage can only be partially compensated for by the addition of entraining agents to CO 2 , the additional control outlay for the entraining agent dosing being regarded as a further disadvantage.

Außer CO2 wurde auch schon verdichtetes Propan als Lösemittel für die Extraktion von Fetten und Ölen empfohlen. So wird gemäß der DE-OS 28 43 920 die Raffination von rohen pflanzlichen Fetten und Ölen mit überkritischen Gasen wie Propan und CO2 vorgenommen, während in anderen Druckschriften (US-PS 4 331 695 = DE-OS 23 63 418, US-PS 3 939 281, DE-OS 22 55 567, DE-OS 22 55 566) ein Extraktionsdruck nahe oder oberhalb des kritischen Druckes und unterkritische Extraktionstemperaturen empfohlen werden. Die kritischen Bedingungen von Propan sind ≥ 42 bar und ≥ 97°C. Gemäß der US-PS 2 560 935 bzw. US-PS 2 682 551 wird flüssiges Propan als Lösemittel für Öle und Fette offenbart, doch werden keine spezifischen Angaben hinsichtlich des Extraktionsdruckes gemacht. Schließlich wird gemäß der US-PS 2 254 245 eine Fettextraktion bei sehr niedrigen Temperaturen (< 0°C) beschrieben, während gemäß der US-PS 1 802 533 ein maximaler Extraktionsdruck von 7 bar empfohlen wird. Kritische Zustandsparameter wurden außerdem oftmals bei der Abscheidung der extrahierten Lipide gewählt, wobei man in diesem Zustandsbereich eine Phasentrennung in eine ölreiche und eine ölarme Propanphase ausnutzt, um das Öl abzutrennen oder zu fraktionieren (vgl. beispielsweise US-PS 2 660 590 oder US-PS 2 548 434).In addition to CO 2 , compressed propane was also recommended as a solvent for the extraction of fats and oils. Thus, according to DE-OS 28 43 920, the refining of raw vegetable fats and oils with supercritical gases such as propane and CO 2 is carried out, while in other publications (US Pat. No. 4,331,695 = DE-OS 23 63 418, US Pat 3 939 281, DE-OS 22 55 567, DE-OS 22 55 566) an extraction pressure near or above the critical pressure and subcritical extraction temperatures be recommended. The critical conditions for propane are ≥ 42 bar and ≥ 97 ° C. According to US Pat. No. 2,560,935 and US Pat. No. 2,682,551, liquid propane is disclosed as a solvent for oils and fats, but no specific statements are made regarding the extraction pressure. Finally, a fat extraction at very low temperatures (<0 ° C.) is described according to US Pat. No. 2,254,245, while a maximum extraction pressure of 7 bar is recommended according to US Pat. No. 1,802,533. Critical state parameters were also often chosen for the separation of the extracted lipids, in which state phase separation into an oil-rich and an oil-poor propane phase is used in order to separate or fractionate the oil (see, for example, US Pat. No. 2,660,590 or US Pat 2 548 434).

In der US-A-5041245 wird zum Zwecke der Extraktion von ölhaltigen pflanzlichen Materialien, wie Reiskleie, durch kontinuierliche Arbeitsweise ohne besonderen Energieaufwand gelehrt, ein sogenanntes Verdichtungs- und Plastifizierungsprinzip anzuwenden, bei welchem das Extraktionsgut mit Hilfe von Schneckenförderern kompaktiert und anschließend durch Zusatz eines flüssigen Versiegelungsmittels in eine plastische Masse überführt wird, die bessere Transporteigenschaften aufweist. Die Verdichtungs- und Plastifizierungsmittel bestehen im Prinzip aus einer Förderschnecke. Dieses Verfahren eignet sich nur für Naturstoffe, bei denen ein gasdichter Transport über die Förderschnecke in die Extraktionsanlage sichergestellt ist. Außerdem muß der Extrakt aus dem Lösemittel durch eine Erhöhung von Druck und Temperatur bis nahe an die kritische Temperatur abgetrennt werden, worauf sich noch eine mehrstufige Abscheidung durch Druckabsenkung anschließt. Das Verfahren ist daher recht aufwendig und außerdem nur für solche Naturstoffe anwendbar, die in der beschriebenen Weise so verdichtet und plastifiziert werden können, daß ein gasdichter Transport sichergestellt ist.In the US-A-5041245 for the extraction of oil-containing plant materials, such as rice bran, is taught by continuous operation without special energy expenditure to apply a so-called compression and plasticization principle, in which the extraction material is compacted with the aid of screw conveyors and then by adding one liquid sealant is converted into a plastic mass that has better transport properties. The compaction and plasticizing agents basically consist of a screw conveyor. This process is only suitable for natural substances where gas-tight transport via the screw conveyor into the extraction system is ensured. In addition, the extract from the solvent must be separated by increasing the pressure and temperature up to the critical temperature, which is followed by a multi-stage separation by lowering the pressure. The method is therefore quite complex and, moreover, can only be used for those natural substances which can be compressed and plasticized in the manner described so that gas-tight transport is ensured.

Diese bekannten Verfahren sind alle mit Nachteilen behaftet: Zum einen werden bei kritischen und überkritischen Zustandsbedingungen Extraktionsergebnisse erzielt, bei der die Qualität des extrahierten Öles oder Fettes durch hohe thermische Belastung starkt gemindert wird. Zum anderen ist in Druckbereichen von < 10 bar die Extraktion mit flüssigem Propan zwar selektiv, doch ist der Stoffübergang bei der Extraktion limitiert, so daß längere Extraktionszeiten und größere Extraktionsmittelmengen erforderlich sind, um das Extraktionsziel der Entfettung oder Entölung zu erreichen.These known methods all have disadvantages: on the one hand, extraction results are achieved under critical and supercritical condition conditions, in which the quality of the extracted oil or fat is severely reduced by high thermal stress. On the other hand, the extraction with liquid propane is selective in pressure ranges of <10 bar, but the mass transfer during the extraction is limited, so that longer extraction times and larger amounts of extractant are required in order to achieve the extraction goal of degreasing or oil removal.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zur Extraktion von Fetten und Ölen aus Naturstoffen mit Hilfe von Propan als Lösemittel zu entwickeln, welches die genannten Nachteile des Standes der Technik nicht aufweist, welches ohne großen technischen Aufwand sowohl eine ausreichende Gasbeladung mit Fetten und Ölen als auch eine gute sensorische Qualität der Produkte ermöglicht.The present invention was therefore based on the object of developing a process for the extraction of fats and oils from natural substances with the aid of propane as a solvent, which does not have the disadvantages of the prior art mentioned and which, without great technical outlay, has both sufficient gas loading with fats and oils as well as a good sensory quality of the products.

Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß man die Extraktion bei einem Druck von 10 bis 30 bar und einer Temperatur von 10 bis 55°C durchführt und die Abscheidung der extrahierten Fette und Öle vom Lösemittel durch Druckerniedrigung oder/und Temperaturerhöhung bis ≤ 80°C vornimmt. Es hat sich nämlich überraschenderweise gezeigt, daß man bei diesem relativ engen Druck- und Temperaturbereich optimale Bedingungen für die Extraktion von Fetten und Ölen mit flüssigem Propan vorfindet, weil nicht nur gute Extraktausbeuten, sondern auch qualitativ hochwertige Extrakte gewonnen werden, die keine oder nur geringe Mengen an unerwünschten Begleitstoffen enthalten. Dies ist deshalb so überraschend, weil man verdichteten Gasen in flüssigem (unterkritischem) Zustand i.a. ungünstigere Extraktionseigenschaften zubilligt als beispielsweise Gasen im kritischen oder überkritischen Zustand. Zudem wird ein unnötig hoher Extraktionsdruck (> 30 bar) vermieden, wodurch die Investitions- und Betriebskosten deutlich reduziert werden können.This object was achieved in that the extraction is carried out at a pressure of 10 to 30 bar and a temperature of 10 to 55 ° C and the separation of the extracted fats and oils from the solvent by reducing the pressure and / or increasing the temperature to ≤ 80 ° C makes. Surprisingly, it has been shown that optimal conditions for the extraction of fats and oils with liquid propane are found in this relatively narrow pressure and temperature range, because not only good extract yields but also high-quality extracts are obtained which have little or no results Contain quantities of unwanted accompanying substances. This is so surprising because compressed gases are generally in a liquid (subcritical) state. Admitted less favorable extraction properties than, for example, gases in the critical or supercritical state. In addition, an unnecessarily high extraction pressure (> 30 bar) is avoided, which can significantly reduce investment and operating costs.

Für das erfindungsgemäße Verfahren können im Prinzip alle fett- oder ölhaltigen Naturstoffe auf pflanzlicher, tierischer oder mikrobieller Basis eingesetzt werden. Beispiele für pflanzliche Fette oder Öle sind Olivenöl, Palmöl, Bambusfett, Kokosfett, Kakaobutter, Kaffeeöle, Erdnußbutter, Rapsöl (Rüböl), Flachsöl (Leinöl), Sonnenblumenöl, Weizenkeimöl, Reiskeimöl, Baumwollsaatöl, Maiskeimöl, Sojaöl, Palmkernöl sowie Kürbiskernöl. Als tierische Produkte kommen beispielsweise Rind- oder Kalbfleisch sowie Seetieröle wie z.B. Fischöle in Frage. Schließlich kann das erfindungsgemäße Verfahren auch für Fermentationsrückstände beispielsweise aus Hefen, Pilzen oder Bakterien herangezogen werden.In principle, all fat-containing or oil-containing natural substances based on plants, animals or microbes can be used for the process according to the invention. Examples of vegetable fats or oils are olive oil, palm oil, bamboo fat, coconut fat, cocoa butter, coffee oils, peanut butter, rapeseed oil (rapeseed oil), flax oil (linseed oil), sunflower oil, wheat germ oil, rice germ oil, cottonseed oil, corn germ oil, soybean oil, palm kernel oil and pumpkin seed oil. For example, beef or veal and marine oils such as e.g. Fish oils in question. Finally, the method according to the invention can also be used for fermentation residues, for example from yeasts, fungi or bacteria.

Zur Erhöhung der Extraktionsausbeute empfiehlt es sich, das Extraktionsgut in zerkleinerter, pelletierter Form einzusetzen. Sollte das (insbesondere feste) Ausgangsmaterial einen hohen Wassergehalt aufweisen, wie z.B. Fleisch oder Fermentationsrückstände, so hat es sich als besonders vorteilhaft erwiesen, die Feuchte durch geeignete Trocknungsmethoden vor der Extraktions auf unter 50 % zu reduzieren.To increase the extraction yield, it is advisable to use the extraction material in comminuted, pelletized form. Should the (in particular solid) starting material have a have a high water content, such as meat or fermentation residues, it has proven to be particularly advantageous to reduce the moisture to below 50% by suitable drying methods before the extraction.

Es ist als erfindungswesentlich anzusehen, daß die Extraktion mit flüssigem Propan in einem sehr engen und definierten Druck- und Temperaturbereich durchgeführt wird, der bei 10 bis 30 bar bzw. 10 bis 55°C liegt. Vorzugsweise wird bei einem Extraktionsdruck von 15 bis 25 bar und einer Extraktionstemperatur von 20 bis 45°C gearbeitet. In jedem Fall müssen Extraktionsdruck und -temperatur so aufeinander abgestimmt werden, daß das Propan in flüssigem Zustand vorliegt.It is to be regarded as essential to the invention that the extraction with liquid propane is carried out in a very narrow and defined pressure and temperature range which is 10 to 30 bar or 10 to 55 ° C. The process is preferably carried out at an extraction pressure of 15 to 25 bar and an extraction temperature of 20 to 45 ° C. In any case, the extraction pressure and temperature must be coordinated so that the propane is in a liquid state.

Bei Drucken > 30 bar werden die Extraktionseigenschaften des flüssigen Propans insbesondere bei der Extraktion von Ölsaaten zunehmend unselektiv, d.h. es werden auch unerwünschte Farbstoffe und unverseifbare Anteile mitextrahiert, wodurch die Qualität des extrahierten Öles stark gemindert wird. Mit steigender Extraktionstemperatur (nahe oder über TK) besteht zudem die Gefahr, daß insbesondere bei Ölen mit einem hohen Gehalt an mehrfach ungesättigten Fettsäuren zum einen unerwünschte Reaktionen in der komplexen Naturstoffmatrix des Ausgangsmaterials auftreten (und dadurch die Extraktausbeute sinkt) und zum anderen unerwünschte Isomerisierungen an den Doppelbindungen der mehrfach ungesättigten Fettsäuren (Entstehung von cis, trans-konjugierten Doppelbindungen) zu beobachten sind, die den ernährungsphysiologischen Wert des Produktes negativ beeinflussen.At pressures> 30 bar, the extraction properties of the liquid propane become increasingly unselective, particularly when extracting oilseeds, ie unwanted dyes and unsaponifiable fractions are also extracted, which greatly reduces the quality of the extracted oil. With increasing extraction temperature (near or above T K ), there is also the risk that, in particular with oils with a high content of polyunsaturated fatty acids, undesirable reactions occur in the complex natural product matrix of the starting material (and the extract yield drops as a result) and, on the other hand, undesirable isomerizations The double bonds of polyunsaturated fatty acids (formation of cis, trans-conjugated double bonds) can be observed, which have a negative impact on the nutritional value of the product.

Die eingesetzte Propangasmenge kann in weiten Grenzen variiert werden und richtet sich im wesentlichen nach der Menge des zu extrahierenden Öles oder Fettes. Je nach Art des Ausgangsmaterials sind normalerweise pro g zu extrahierendes Fett oder Öl 2,5 bis 500 g flüssiges Propan erforderlich. Die maximale Gasbeladung mit lipiden Stoffen beträgt unter diesen Extraktionsbedingungen je nach Art des extrahierten Fettes oder Öles 5 bis 25 Gew.-%.The amount of propane gas used can be varied within wide limits and depends essentially on the amount of oil or fat to be extracted. Depending on the type of raw material, 2.5 to 500 g of liquid propane are normally required per g of fat or oil to be extracted. The maximum gas loading with lipid substances under these extraction conditions is 5 to 25% by weight, depending on the type of fat or oil extracted.

Die Reinheit des eingesetzten Propangases ist in den meisten Fällen relativ unkritisch, d.h. es können auch noch merkliche Mengen an Verunreinigungen homologer Kohlenwasserstoffe (bedingt durch den Raffinationsprozeß) zugegen sein, ohne daß es zu merklichen Qualitätseinbußen kommt. Vorzugsweise wird Propan in technischer Reinheit von ca. 90 % und in desodorierter Form eingesetzt. Die Extraktion mit flüssigem Propan kann zur vollständigen Gewinnung der Fette oder Öle in manchen Fällen auch in zwei oder mehr Stufen durchgeführt werden.The purity of the propane gas used is relatively uncritical in most cases, i.e. noticeable amounts of impurities from homologous hydrocarbons (due to the refining process) can also be present without any noticeable loss in quality. Propane is preferably used in technical purity of approx. 90% and in deodorized form. The extraction with liquid propane can in some cases also be carried out in two or more stages in order to obtain the fats or oils completely.

Das Propangas wird vorzugsweise im Kreis geführt, um sich mehrfach mit den gewünschten lipiden Stoffen beladen zu können, doch ist es auch möglich, das Extraktionsgut nur einmal mit dem Extraktionsmedium zu kontaktieren. Um eine hohe Wirtschaftlichkeit des Verfahrens zu erzielen, können mehrere Extraktionsautoklaven in Reihe geschaltet und nacheinander vom Extraktionsmedium durchströmt werden. Durch eine geeignete Schaltung der Reihenfolge dieser Autoklaven (z.B. Durchströmung nach fortgeschrittenem Extraktionsgrad) kann die maximal erreichbare Gasbeladung des flüssigen Propans stets optimal ausgenutzt werden.The propane gas is preferably circulated in order to be able to load the desired lipid substances several times, but it is also possible to contact the extraction material only once with the extraction medium. In order to achieve a high economic efficiency of the process, several extraction autoclaves can be connected in series and the extraction medium can be flowed through in succession. The maximum achievable gas load of the liquid propane can always be optimally used by suitably switching the sequence of these autoclaves (e.g. flow through according to the advanced degree of extraction).

Im Anschluß an die Extraktion werden im flüssigen Propan gelöste Fette und Öle durch eine Druckerniedrigung oder/und Temperaturerhöhung abgeschieden, wobei sich eine Druckerniedrigung und eine Temperaturerhöhung auf ≤ 80°C als besonders vorteilhaft erwiesen hat. Auf diese Weise wird sichergestellt, daß keine unerwünschten Reaktionen wie z.B. Isomerisierungen der Doppelbindungen von mehrfach ungesättigten Fettsäuren während der Abscheidung stattfinden. Gemäß einer bevorzugten Ausführungsform erfolgt die Abscheidung durch isobare Verdampfung des Lösemittels, wodurch die Wirtschaftlichkeit des Verfahrens entscheidend erhöht werden kann.Following the extraction, fats and oils dissolved in the liquid propane are separated by reducing the pressure and / or increasing the temperature, a reduction in pressure and an increase in temperature to 80 80 ° C. having proven particularly advantageous. In this way it is ensured that no undesired reactions such as isomerization of the double bonds of polyunsaturated fatty acids take place during the deposition. According to one In a preferred embodiment, the deposition is carried out by isobaric evaporation of the solvent, as a result of which the economy of the process can be increased significantly.

Mit Hilfe des erfindungsgemäßen Verfahrens lassen sich qualitativ hochwertige Produkte im Hinblick auf Farbe, Geruch bzw. Geschmack in guter Ausbeute und unter schonenden Bedingungen gewinnen. Wegen des vergleichsweise geringen technischen Aufwandes ist dieses Verfahren außerdem gut für die Anwendung im technischen Maßstab geeignet.With the aid of the method according to the invention, high-quality products with regard to color, smell or taste can be obtained in good yield and under gentle conditions. Because of the comparatively low technical complexity, this method is also well suited for use on an industrial scale.

Die nachfolgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

BeispieleExamples Beispiel 1example 1

200 g vorentfetteter Kakao (Granulat in 1 bis 2 mm Größe, Fettgehalt ca. 11 %) wurden im Druckautoklaven bei 20 bar und 25°C mit verdichtetem Propan im Abstrom extrahiert. Nach Durchfluß von 1 kg Propan wurde bei kontinuierlicher Entspannung des Gases auf Atmosphärendruck keine Kakaobutter mehr abgeschieden. Der Restfettgehalt im Granulat war < 0,3 %, die Ausbeute an extrahierter Kakaobutter betrug 2,2 g.200 g of pre-defatted cocoa (granules 1 to 2 mm in size, fat content approx. 11%) were extracted in a pressure autoclave at 20 bar and 25 ° C with compressed propane in the outflow. After 1 kg of propane had flowed through, the cocoa butter was no longer separated while the gas was continuously depressurized to atmospheric pressure. The residual fat content in the granules was <0.3%, the yield of extracted cocoa butter was 2.2 g.

Beispiel 2Example 2

140 g zermahlene Flachssamen (Ölgehalt ca. 41 %) wurden im Druckautoklaven bei 20 bar und 25°C mit verdichtetem Propan im Abstrom extrahiert. Nach Durchfluß von 0,7 kg Propan wurden 50 g Öl extrahiert (entspricht einer 87 %igen Entfettung). Nach einer zweiten Vermahlung des Rückstandes (Fettgehalt ca. 8 %) wurde mit weiteren 0,15 kg Propan unter gleichen Bedingungen extrahiert, wobei eine nahezu vollständige Entölung des Rückstandes erzielt wurde. Die Abscheidung des Öles erfolgte in beiden Stufen durch kontinuierliche Entspannung des Gases auf Atmosphärendruck. Ein Restölgehalt im Rückstand konnte mit Soxhlet-Extraktion mit Hexan (8 h) nicht festgestellt werden, die Ausbeute an Öl betrug 57,5 g.140 g of ground flaxseed (oil content approx. 41%) were extracted in a pressure autoclave at 20 bar and 25 ° C with compressed propane in the outflow. After 0.7 kg of propane had flowed through, 50 g of oil were extracted (corresponds to an 87% degreasing). After a second grinding of the residue (fat content approx. 8%), extraction was carried out with a further 0.15 kg of propane under the same conditions, an almost complete one The residue was deoiled. The oil was separated in both stages by continuously releasing the gas to atmospheric pressure. A residual oil content in the residue could not be determined with Soxhlet extraction with hexane (8 h), the yield of oil was 57.5 g.

Beispiel 3Example 3

1 kg vorbehandelte Sojaflocken (Ölgehalt ca. 18 %) wurden im Druckautoklaven bei 30 bar und 45°C mit verdichtetem Propan extrahiert. Das Extraktionsmittel wurde kontinuierlich im Kreis geführt, wobei die Abscheidung des Öls durch isobare Verdampfung des Propans bei 80°C im Abscheider erfolgte, bevor das unbeladene Propan (gekühlt auf 45°C) das Extraktionsgut erneut durchströmte. Nach einer Gesamtmenge von 7 kg Propan, die die Sojaflocken durchströmte, wurde die Extraktion beendet. Der Restölgehalt des Rückstands lag unter 1 %, die Ausbeute an Öl waren 175 g.1 kg of pretreated soy flakes (oil content approx. 18%) were extracted in a pressure autoclave at 30 bar and 45 ° C with compressed propane. The extractant was continuously circulated, the oil being separated by isobaric evaporation of the propane at 80 ° C. in the separator before the unloaded propane (cooled to 45 ° C.) again flowed through the extraction material. After a total of 7 kg of propane flowing through the soy flakes, the extraction was stopped. The residual oil content of the residue was less than 1%, the oil yield was 175 g.

Beispiel 4Example 4

350 g mechanisch vorentfetteter und mittels Gefriertrocknung auf einen Wassergehalt von ca. 20 % eingestellter Fleischpellets (Größe 0,5 bis 1,5 cm, Fettgehalt i.Tr. 25 %) wurden im Druckautoklaven bei 25 bar und 40°C mit 1,75 kg verdichtetem Propan extrahiert. Im Kreisprozeß (analog Beispiel 3) erfolgte die Fettabscheidung isobar durch Temperaturerhöhung auf 75°C. Der Fettgehalt im Extraktionsrückstand wurde mittels Soxhlet (8 h mit Hexan) bei 3 % i.Tr. bestimmt; im Abscheider wurden 65 g Fett gesammelt.350 g of mechanically pre-degreased meat pellets (size 0.5 to 1.5 cm, fat content usually 25%) adjusted to a water content of approx. 20% by means of freeze drying in a pressure autoclave at 25 bar and 40 ° C with 1.75 kg of compressed propane extracted. In the cyclic process (analogous to Example 3), the fat was isobarically separated by increasing the temperature to 75 ° C. The fat content in the extraction residue was determined using Soxhlet (8 h with hexane) at 3% i.Tr. certainly; 65 g of fat were collected in the separator.

Claims (8)

  1. Process for the extraction of fats and oils from natural products with the aid of liquid propane as the solvent,
    wherein
    the extraction is carried out at a pressure of 10 to 30 bar and a temperature of 10 to 55°C and the separation of the extracted fats and oils from the solvent is carried out by lowering the pressure or/and increasing the temperature to ≤ 80°C.
  2. Process as claimed in claim 1,
    wherein
    the extraction is carried out at a pressure of 15 to 25 bar and a temperature of 20 to 45°C.
  3. Process as claimed in claim 1 or 2,
    wherein
    the separation is carried out by isobaric evaporation of the solvent.
  4. Process as claimed in one of the claims 1 to 3,
    wherein
    the starting material containing fat or oil is used in a granulated or pelleted form.
  5. Process as claimed in one of the claims 1 to 4,
    wherein
    the amount of liquid propane used is 2.5 to 500 g per g of the fat or oil to be extracted.
  6. Process as claimed in one of the claims 1 to 5,
    wherein
    the content of fats and oils in the gas is 5 to 25 % by weight.
  7. Process as claimed in one of the claims 1 to 6,
    wherein
    liquid propane is used in technical purity (ca. 90 %) and in a deodorized form.
  8. Process as claimed in one of the claims 1 to 7,
    wherein
    the extraction is carried out in several extraction autoclaves connected in series.
EP93116266A 1992-10-08 1993-10-07 Process for the extraction of fats and oils Expired - Lifetime EP0591981B1 (en)

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DE4233911 1992-10-08
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EP0591981A1 (en) 1994-04-13
ATE146216T1 (en) 1996-12-15
US5405633A (en) 1995-04-11
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RU2062295C1 (en) 1996-06-20
ES2097415T3 (en) 1997-04-01
JPH06207193A (en) 1994-07-26

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