EP0363971A2 - Process for separating terpenes from essential oils - Google Patents

Process for separating terpenes from essential oils Download PDF

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Publication number
EP0363971A2
EP0363971A2 EP89119001A EP89119001A EP0363971A2 EP 0363971 A2 EP0363971 A2 EP 0363971A2 EP 89119001 A EP89119001 A EP 89119001A EP 89119001 A EP89119001 A EP 89119001A EP 0363971 A2 EP0363971 A2 EP 0363971A2
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Prior art keywords
adsorbent
extraction
terpenes
essential oils
bar
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EP89119001A
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German (de)
French (fr)
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EP0363971B1 (en
EP0363971A3 (en
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Jan Dr. Cully
Erwin Dr. Schütz
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
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/022—Refining

Definitions

  • the present invention relates to a process for removing terpenes from essential oils in a three-step process.
  • Essential oils are important aroma carriers in the food industry. For example, cold-pressed oils from citrus fruits are widely used for the production of essences for the beverage industry and for the flavoring of baked goods. These essential oils often contain terpene hydrocarbons from the mono- and sesquiterpene series, which have only limited storage stability and are thermolabile and, moreover, have a lower flavor intensity than the actual flavoring substances, which are predominantly derived from volatile oxygen-containing compounds such as aldehydes, ketones, esters, acids, phenols, alcohols and Put lactones together. For these reasons, the removal of the terpenes is an important step to improve the storage stability and to increase the aroma intensity of essential oils.
  • a number of processes for the de-terpenization of essential oils which use differences in the vapor pressure, in the polarity or in the solubility of the terpene components in comparison with the oxygen-containing compounds to separate the terpenes. All of these processes have certain disadvantages, which are reflected either in the product quality, in the process costs or in the yield. For example, it has been described to dissolve essential oils in aqueous alcohols, whereby separate the terpenes and then obtain the desired aroma fractions by salting out or liquid-liquid extraction. The separation effect and the yield in these processes are unsatisfactory. Depending on the type of extractant used, technical or environmental problems can also occur.
  • US Pat. No. 4,647,466 discloses a process for extracting volatile oxygen-containing substances such as ethyl butyrate or hexanal from citrus oils with the aid of compressed gases, enriching limonene. Since citrus oils such as Orange oils, however, consist of up to 95% limonene, very large amounts of CO2 or long extraction times are required to carry out the process in order to remove a high proportion of limonene with the necessary selectivity from the aromatic oil.
  • the present invention was therefore based on the object of developing a process for removing terpenes from essential oils which does not have the disadvantages of the prior art mentioned, but rather a selective enrichment of the essential oils with good yields with little technical effort and under gentle conditions enables.
  • the method according to the present invention consists of at least three stages.
  • a polar solid (adsorbent) a polar solid (adsorbent).
  • all terpene-containing essential oils can be used in the context of the present invention.
  • Citrus oils obtained from citrus fruits such as oranges, lemons, mandarins, limes, limes, grapefruit or cravos are particularly suitable.
  • other aromatic oils such as hop, clove, laurel, ginger, peppermint or cedarwood oil can also be used.
  • CO2 extracts or oleoresins can also be used.
  • the essential oils have a terpene content of up to 95%.
  • the adsorbent can be loaded with the essential oil by the known methods, e.g. simply by mixing.
  • Common polar solids such as e.g. Silica gel, aluminum oxide, diatomaceous earth, cellulose, bentonite, magnesium silicates etc. can be used. Silica gel and aluminum oxide have proven to be particularly advantageous.
  • the amount of polar adsorbent can be varied within wide limits, but preferably 10 to 60% by weight of polar adsorbent are used, based on the starting amount of essential oil. With this loading of the adsorbent according to stage a), the oxygen-containing aroma substances are largely adsorbed on the solid, while the terpenes largely remain in the liquid phase. Depending on the type of aroma oil used and the amount of adsorbent used, about 60 to 95% of the aroma substances are adsorbed.
  • the adsorbent loaded with the aroma substances is then separated from the terpenes remaining in the liquid phase.
  • the methods customary in technology for separating solids and liquids can be used here. Because of the quick and complete separation centrifugation is preferably used according to the invention. However, it is readily possible to use other separation processes such as filtration at this stage. In this way, the majority of the terpenes contained in the essential oils can usually be removed without noticeable losses in the valuable aroma substances.
  • the adsorbent can be used several times for adsorption. It is possible to increase the yield of aromas during adsorption by first mixing and separating the adsorbent with the terpene fraction from a previous batch as described above. In this case, the mixture of terpene fraction and adsorbent can be poured into a column and the essential oil to be enriched can be passed through in a type of column chromatography.
  • the adsorbent loaded with aroma component is subjected to a high pressure extraction with compressed CO2, the aroma substances being desorbed or extracted.
  • the high pressure extraction should take place at pressures above 70 bar and temperatures from 10 to 80 ° C in order to achieve a complete extraction of the aroma substances.
  • the preferred extraction conditions are pressures of> 100 bar, in particular from 200 to 300 bar and / or temperatures from 30 to 70 ° C., because the aroma substances are obtained particularly quickly and gently under these conditions. It is clear that in addition to the desired flavoring substances, this high-pressure extraction also extracts the rest of the terpenes, which was also adsorbed onto the polar adsorbent in the first stage.
  • a pre-extraction is carried out in a preferred embodiment before the high-pressure extraction (step c) in order to obtain the flavorings performed, in which the remaining terpenes are first removed from the adsorbent.
  • This pre-extraction is also carried out with compressed carbon dioxide, but in contrast to the process conditions of stage c) (main extraction) at pressures below 100 bar, preferably at 70 to 90 bar.
  • the temperature range for the pre-extraction is 30 to 80 ° C, preferably 50 to 70 ° C.
  • a largely selective extraction of the terpenes takes place under these process conditions, while the aroma substances remain on the adsorbent.
  • the terpene hydrocarbon content of these pre-extracts is generally higher than the terpene content of the starting oil.
  • This pre-extraction is followed, as already described, by the main extraction (stage c), in which the oxygen-containing aroma substances are then obtained under gentle conditions.
  • the CO2 aroma extracts obtained in this way can then be completely removed from the CO2 by lowering the density by the usual methods.
  • Example 2 5 kg of orange oil with a lime content of 95.7% were stirred according to Example 1 with 1 kg of silica gel at room temperature for 120 minutes.
  • the loaded silica gel was then separated from the liquid phase by centrifugation and extracted in a high-pressure extraction system with 40 kg of CO2 at 280 bar and 35 ° C. 625 g of concentrate with a lime content of 89.6% were obtained as the extract.
  • the specific CO2 consumption was 8 kg CO2 per kg of starting oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

A process for removing terpenes from essential oils is described and entails a) the terpene-containing essential oils being contacted with a polar solid (adsorbent), b) the loaded adsorbent being separated from the liquid phase enriched in terpenes, and c) the adsorbent loaded with essential oil being extracted with condensed CO2. <??>It is possible in this way substantially to remove the terpenes and, at the same time, to obtain the essential oils in high yield and good quality.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Entfer­nung von Terpenen aus etherischen Ölen in einem dreistufigen Verfahren.The present invention relates to a process for removing terpenes from essential oils in a three-step process.

Etherische Öle stellen wichtige Aromaträger in der Lebensmit­telindustrie dar. So werden beispielsweise kaltgepreßte Öle aus Zitrusfrüchten in großem Umfang zur Herstellung von Es­senzen für die Getränkeindustrie sowie zur Aromatisierung von Backwaren eingesetzt. Häufig enthalten diese etherischen Öle Terpenkohlenwasserstoffe der Mono- und Sesquiterpenreihe, die nur begrenzt lagerstabil sowie thermolabil sind und überdies eine geringere Aromaintensität aufweisen als die eigentlichen Aromastoffe, die sich überwiegend aus flüchtigen sauerstoff­haltigen Verbindungen wie Aldehyden, Ketonen, Estern, Säuren, Phenolen, Alkoholen und Lactonen zusammensetzen. Aus diesen Gründen ist die Entfernung der Terpene ein wichtiger Schritt zur Verbesserung der Lagerstabilität und zur Verstärkung der Aromaintensität von etherischen Ölen.Essential oils are important aroma carriers in the food industry. For example, cold-pressed oils from citrus fruits are widely used for the production of essences for the beverage industry and for the flavoring of baked goods. These essential oils often contain terpene hydrocarbons from the mono- and sesquiterpene series, which have only limited storage stability and are thermolabile and, moreover, have a lower flavor intensity than the actual flavoring substances, which are predominantly derived from volatile oxygen-containing compounds such as aldehydes, ketones, esters, acids, phenols, alcohols and Put lactones together. For these reasons, the removal of the terpenes is an important step to improve the storage stability and to increase the aroma intensity of essential oils.

Außerdem wird durch die Entfernung der unpolaren Terpenkoh­lenwasserstoffe die Wasserlöslichkeit der etherischen Öle verbessert, was insbesondere für die Getränkeindustrie von Bedeutung ist.In addition, the removal of the non-polar terpene hydrocarbons improves the water solubility of the essential oils, which is particularly important for the beverage industry.

Es sind eine Reihe von Verfahren zur Entterpenisierung von etherischen Ölen bekannt, die zur Abtrennung der Terpene Unterschiede im Dampfdruck, in der Polarität oder in der Löslichkeit der Terpenkomponenten im Vergleich zu den sauer­stoffhaltigen Verbindungen ausnutzen. Alle diese Verfahren besitzen gewisse Nachteile, die sich entweder in der Produkt­qualität, in den Verfahrenskosten oder aber in der Ausbeute niederschlagen. So ist beispielsweise beschrieben worden, etherische Öle in wäßrigen Alkoholen aufzulösen, wobei sich die Terpene abscheiden und anschließend die gewünschten Aro­mafraktionen durch Aussalzen oder Flüssig-Flüssig-Extraktion zu gewinnen. Die Trennwirkung und die Ausbeute bei diesen Verfahren sind nicht befriedigend. Außerdem können je nach Art des verwendeten Extraktionsmittels technische oder Umweltprobleme auftreten.A number of processes for the de-terpenization of essential oils are known which use differences in the vapor pressure, in the polarity or in the solubility of the terpene components in comparison with the oxygen-containing compounds to separate the terpenes. All of these processes have certain disadvantages, which are reflected either in the product quality, in the process costs or in the yield. For example, it has been described to dissolve essential oils in aqueous alcohols, whereby separate the terpenes and then obtain the desired aroma fractions by salting out or liquid-liquid extraction. The separation effect and the yield in these processes are unsatisfactory. Depending on the type of extractant used, technical or environmental problems can also occur.

Eine weitere bekannte Methode beispielsweise zur Anreicherung von Zitrusölen stellt die Chromatographie dar. Diese Verfah­ren sind sehr aufwendig und kostspielig, da in stark verdünn­ten Lösungen gearbeitet werden muß. Beim anschließenden Eindampfen der Lösungen besteht außerdem die Gefahr der ther­mischen Zersetzung empfindlicher Inhaltsstoffe oder des Ver­lustes an niedrigsiedenden Aromastoffen.Another known method, for example for the enrichment of citrus oils, is chromatography. These methods are very complex and costly, since work must be carried out in very dilute solutions. When the solutions are subsequently evaporated, there is also a risk of thermal decomposition of sensitive ingredients or of loss of low-boiling aromas.

Weit verbreitet ist die Entfernung von Terpenen mittels Rek­tifikation oder Destillation im Vakuum sowie der Wasserdampf­destillation. Diese Verfahren liefern keine hochwertigen Qualitäten, da die Aromakomponenten durch die thermische Belastung erheblich geschädigt werden.The removal of terpenes by means of rectification or distillation in vacuo and steam distillation is widespread. These processes do not provide high quality, since the aroma components are significantly damaged by the thermal load.

Wesentlich schonender sind hingegen die Verfahren der Hoch­druckextraktion zur Anreicherung von etherischen Ölen, die in jüngster Zeit bekannt geworden sind. So wird beispielsweise in Chem. Ing. Tech. 56, S. 794 (1984) ein Verfahren zur Ent­fernung von Terpenen aus Zitrusölen beschrieben, wobei die Zitrusöle einer Gegenstromextraktion mit Kohlendioxid bei 70 bis 90 bar und ca. 55 bis 85°C in einer Gegenstromkolonne unterworfen werden, an der ein Temperaturgradient angelegt wird. Mit Hilfe der Gegenstromextraktion lassen sich entweder hohe Anreicherungsraten oder hohe Ausbeuten erreichen, aber nicht beides zusammen (vgl. Food Technology, 6, 145 (1988), da entweder die Selektivität des Prozesses gering oder die Beladung des CO₂ mit Terpenen niedrig ist.On the other hand, the processes of high-pressure extraction for the enrichment of essential oils, which have recently become known, are much gentler. For example, in Chem. Ing. Tech. 56 , p. 794 (1984) describes a process for removing terpenes from citrus oils, the citrus oils being subjected to countercurrent extraction with carbon dioxide at 70 to 90 bar and approx. 55 to 85 ° C. in a countercurrent column, to which a temperature gradient is applied . With the help of countercurrent extraction, either high enrichment rates or high yields can be achieved, but not both together (cf. Food Technology, 6 , 145 (1988), since either the selectivity of the process is low or the loading of the CO₂ with terpenes is low.

Schließlich wird in der US-PS 46 47 466 ein Verfahren zur Extraktion von leicht flüchtigen sauerstoffhaltigen Stoffen wie Ethylbutyrat oder Hexanal aus Zitrusölen mit Hilfe von verdichteten Gasen offenbart, wobei Limonen angereichert wird. Da Zitrusöle wie z.B. Orangenöle aber aus bis zu 95 % Limonen bestehen, sind zur Durchführung des Verfahrens sehr große CO₂-Mengen bzw. lange Extraktionszeiten erforderlich, um einen hohen Anteil an Limonen mit der notwendigen Selekti­vität aus dem Aromaöl zu entfernen.Finally, US Pat. No. 4,647,466 discloses a process for extracting volatile oxygen-containing substances such as ethyl butyrate or hexanal from citrus oils with the aid of compressed gases, enriching limonene. Since citrus oils such as Orange oils, however, consist of up to 95% limonene, very large amounts of CO₂ or long extraction times are required to carry out the process in order to remove a high proportion of limonene with the necessary selectivity from the aromatic oil.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zur Entfernung von Terpenen aus etherischen Ölen zu entwickeln, welches die genannten Nachteile des Stan­des der Technik nicht aufweist, sondern mit geringem tech­nischen Aufwand und unter schonenden Bedingungen eine selektive Anreicherung der etherischen Öle mit guten Ausbeu­ten ermöglicht.The present invention was therefore based on the object of developing a process for removing terpenes from essential oils which does not have the disadvantages of the prior art mentioned, but rather a selective enrichment of the essential oils with good yields with little technical effort and under gentle conditions enables.

Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß man

  • a) die terpenhaltigen etherischen Öle mit einem polaren Feststoff (Adsorbens) kontaktiert,
  • b) eine Abtrennung des beladenen Adsorbens von der flüssi­gen, mit Terpenen angereicherten Phase vornimmt und
  • c) das mit etherischem Öl beladene Adsorbens einer Extrak­tion mit verdichtetem CO₂ unterwirft.
This object was achieved in that
  • a) the terpene-containing essential oils are contacted with a polar solid (adsorbent),
  • b) separates the loaded adsorbent from the liquid phase enriched with terpenes and
  • c) the adsorbent loaded with essential oil is subjected to extraction with compressed CO₂.

Es hat sich nämlich überraschenderweise gezeigt, daß man auf diese Weise eine weitgehende Entfernung der Terpene erreicht und gleichzeitig die etherischen Öle in hoher Ausbeute und guter Qualität gewinnen kann.Surprisingly, it has been shown that the terpenes can be largely removed in this way and, at the same time, the essential oils can be obtained in high yield and good quality.

Das Verfahren entsprechend der vorliegenden Erfindung besteht aus mindestens drei Stufen. In der ersten Stufe a) wird das terpenhaltige etherische Öl mit einem polaren Feststoff (Ad­sorbens) kontaktiert. Im Rahmen der vorliegenden Erfindung können im Prinzip alle terpenhaltigen etherischen Öle einge­setzt werden. Hierbei kommen vor allem Zitrusöle in Frage, die aus Zitrusfrüchten wie Orangen, Zitronen, Mandarinen, Limonen, Limetten, Grapefruit oder Cravos gewonnen wurden. Aber auch andere Aromaöle wie Hopfen-, Nelken-, Lorbeer-, Ingwer-, Pfefferminz- oder Zedernholzöl sind einsetzbar. Statt der reinen etherischen Öle können auch CO₂-Extrakte oder Oleoresine verwendet werden. Die etherischen Öle weisen je nach Art und Herkunft Terpengehalte bis zu 95 % auf.The method according to the present invention consists of at least three stages. In the first stage a) terpene-containing essential oil contacted with a polar solid (adsorbent). In principle, all terpene-containing essential oils can be used in the context of the present invention. Citrus oils obtained from citrus fruits such as oranges, lemons, mandarins, limes, limes, grapefruit or cravos are particularly suitable. But other aromatic oils such as hop, clove, laurel, ginger, peppermint or cedarwood oil can also be used. Instead of pure essential oils, CO₂ extracts or oleoresins can also be used. Depending on the type and origin, the essential oils have a terpene content of up to 95%.

Die Beladung des Adsorbens mit dem etherischen Öl kann nach den bekannten Methoden wie z.B. durch einfaches Vermischen erfolgen. Als polare Adsorbenzien können dafür übliche Fest­stoffe, wie z.B. Kieselgel, Aluminiumoxid, Kieselgur, Cellu­lose, Bentonit, Magnesiumsilikate usw., verwendet werden. Kieselgel und Aluminiumoxid haben sich hierbei als besonders vorteilhaft erwiesen.The adsorbent can be loaded with the essential oil by the known methods, e.g. simply by mixing. Common polar solids such as e.g. Silica gel, aluminum oxide, diatomaceous earth, cellulose, bentonite, magnesium silicates etc. can be used. Silica gel and aluminum oxide have proven to be particularly advantageous.

Die Menge des polaren Adsorptionsmittels kann in weiten Gren­zen variiert werden, doch werden vorzugweise 10 bis 60 Gew.-% polares Adsorbens bezogen auf die Ausgangsmenge an etheri­schem Öl eingesetzt. Bei dieser Beladung des Adsorbens gemäß Stufe a) werden die sauerstoffhaltigen Aromastoffe am Fest­stoff größtenteils adsorbiert, während die Terpene weitgehend in der flüssigen Phase verbleiben. Je nach Art des verwende­ten Aromaöls und Menge des eingesetzten Adsorbens werden etwa 60 bis 95 % der Aromastoffe adsorbiert.The amount of polar adsorbent can be varied within wide limits, but preferably 10 to 60% by weight of polar adsorbent are used, based on the starting amount of essential oil. With this loading of the adsorbent according to stage a), the oxygen-containing aroma substances are largely adsorbed on the solid, while the terpenes largely remain in the liquid phase. Depending on the type of aroma oil used and the amount of adsorbent used, about 60 to 95% of the aroma substances are adsorbed.

In der zweiten Stufe b) des erfindungsgemäßen Verfahrens erfolgt dann die Abtrennung des mit den Aromastoffen belade­nen Adsorbens von den in der flüssigen Phase verbliebenen Terpenen. Hierbei können die in der Technik üblichen Methoden zur Trennung von Feststoffen und Flüssigkeiten angewendet werden. Wegen der raschen und vollständigen Trennung wird hierbei die Zentrifugation erfindungsgemäß bevorzugt einge­setzt. Es ist jedoch ohne weiteres möglich, bei dieser Stufe andere Trennverfahren wie z.B. die Filtration heranzuziehen. Auf diese Weise kann in der Regel bereits der Hauptanteil der in den etherischen Ölen enthaltenen Terpene entfernt werden, ohne daß es zu merklichen Verlusten an den wertvollen Aroma­stoffen kommt.In the second stage b) of the process according to the invention, the adsorbent loaded with the aroma substances is then separated from the terpenes remaining in the liquid phase. The methods customary in technology for separating solids and liquids can be used here. Because of the quick and complete separation centrifugation is preferably used according to the invention. However, it is readily possible to use other separation processes such as filtration at this stage. In this way, the majority of the terpenes contained in the essential oils can usually be removed without noticeable losses in the valuable aroma substances.

Im allgemeinen kann das Adsorbens mehrfach für die Adsorption eingesetzt werden. Es ist möglich, die Ausbeute an Aromastof­fen bei der Adsorption zu erhöhen, indem man zunächst das Adsorbens mit der Terpenfraktion einer vorhergehenden Charge mischt und abtrennt wie vorhergehend beschrieben. In diesem Fall kann man das Gemisch aus Terpenfraktion und Adsorbens in eine Säule einfüllen und das anzureichernde etherische Öl in einer Art Säulen-Chromatographie hindurchleiten.In general, the adsorbent can be used several times for adsorption. It is possible to increase the yield of aromas during adsorption by first mixing and separating the adsorbent with the terpene fraction from a previous batch as described above. In this case, the mixture of terpene fraction and adsorbent can be poured into a column and the essential oil to be enriched can be passed through in a type of column chromatography.

Bei der nachfolgenden dritten Stufe c) wird das mit Aromakom­ponente beladene Adsorbens einer Hochdruckextraktion mit verdichtetem CO₂ unterworfen, wobei die Aromastoffe desor­biert bzw. extrahiert werden. Die Hochdruckextraktion sollte bei Drucken oberhalb von 70 bar und Temperaturen von 10 bis 80°C erfolgen, um eine vollständige Extraktion der Aromastof­fe zu erreichen. Als bevorzugte Extraktionsbedingungen sind Drucke von >100 bar, insbesondere von 200 bis 300 bar und/oder Temperaturen von 30 bis 70°C anzusehen, weil unter diesen Bedingungen die Aromastoffe besonders rasch und scho­nend gewonnen werden. Es ist klar, daß man bei dieser Hoch­druckextraktion außer den gewünschten Aromastoffen auch den Rest an Terpenen mitextrahiert, der bei der ersten Stufe an das polare Adsorbens mitadsorbiert wurde.In the subsequent third stage c) the adsorbent loaded with aroma component is subjected to a high pressure extraction with compressed CO₂, the aroma substances being desorbed or extracted. The high pressure extraction should take place at pressures above 70 bar and temperatures from 10 to 80 ° C in order to achieve a complete extraction of the aroma substances. The preferred extraction conditions are pressures of> 100 bar, in particular from 200 to 300 bar and / or temperatures from 30 to 70 ° C., because the aroma substances are obtained particularly quickly and gently under these conditions. It is clear that in addition to the desired flavoring substances, this high-pressure extraction also extracts the rest of the terpenes, which was also adsorbed onto the polar adsorbent in the first stage.

Will man deshalb eine praktisch vollständige Entfernung der Terpene aus den etherischen Ölen erreichen, wird in einer bevorzugten Ausführungsform vor der Hochdruckextraktion (Stu­fe c) zur Gewinnung der Aromastoffe eine Vorextraktion durch­ geführt, bei der zunächst die restlichen Terpene aus dem Adsorptionsmittel entfernt werden. Diese Vorextraktion wird ebenfalls mit verdichetem Kohlendioxid durchgeführt, doch im Gegensatz zu den Verfahrensbedingungen der Stufe c) (Hauptex­traktion) bei Drucken unterhalb von 100 bar, vorzugsweise bei 70 bis 90 bar.If it is therefore desired to achieve a virtually complete removal of the terpenes from the essential oils, a pre-extraction is carried out in a preferred embodiment before the high-pressure extraction (step c) in order to obtain the flavorings performed, in which the remaining terpenes are first removed from the adsorbent. This pre-extraction is also carried out with compressed carbon dioxide, but in contrast to the process conditions of stage c) (main extraction) at pressures below 100 bar, preferably at 70 to 90 bar.

Der Temperaturbereich für die Vorextraktion beträgt 30 bis 80°C, vorzugsweise 50 bis 70°C. Unter diesen Verfahrensbedin­gungen findet eine weitgehend selektive Extraktion der Terpe­ne statt, während die Aromastoffe auf dem Adsorbens zurück­bleiben. Der Terpenkohlenwasserstoff-Gehalt dieser Vorextrak­te liegt im allgemeinen über dem Terpengehalt des Ausgangs­öls. An diese Vorextraktion schließt sich dann, wie bereits beschrieben, die Hauptextraktion (Stufe c) an, bei der dann die sauerstoffhaltigen Aromastoffe unter schonenden Bedingun­gen gewonnen werden. Die auf diese Weise erhaltenen CO₂-Aro­maextrakte lassen sich dann nach den üblichen Methoden durch Dichteerniedrigung vom CO₂ restlos befreien. Auf diese Weise ist es mgölich, hochkonzentrierte Extrakte von etherischen Ölen mit niedrigen Terpengehalten (Reduktion der Terpene bis zu 95 %) in hoher Ausbeute zu gewinnen, die wegen der scho­nenden Behandlung eine sehr gute Qualität aufweisen. Da die Hauptmenge der Terpene bereits vor der CO₂-Extraktion ent­fernt wird, sind für die Extraktion der wichtigen Aromastoffe nur noch vergleichsweise geringe Mengen an CO₂ erforderlich.The temperature range for the pre-extraction is 30 to 80 ° C, preferably 50 to 70 ° C. A largely selective extraction of the terpenes takes place under these process conditions, while the aroma substances remain on the adsorbent. The terpene hydrocarbon content of these pre-extracts is generally higher than the terpene content of the starting oil. This pre-extraction is followed, as already described, by the main extraction (stage c), in which the oxygen-containing aroma substances are then obtained under gentle conditions. The CO₂ aroma extracts obtained in this way can then be completely removed from the CO₂ by lowering the density by the usual methods. In this way it is possible to obtain highly concentrated extracts of essential oils with low terpene contents (reduction of the terpenes up to 95%) in high yield, which are of very good quality due to the gentle treatment. Since the majority of the terpenes are removed before the CO₂ extraction, only comparatively small amounts of CO₂ are required for the extraction of the important aromatic substances.

Die nachfolgenden Beispiele sollen die Erfindung näher erläu­tern, ohne sie jedoch darauf zu beschränken.The following examples are intended to explain the invention in more detail, but without restricting it thereto.

Beispiel 1example 1 Gewinnung von terpenarmem Zitronen-SchalenölkonzentratExtraction of low-terpene lemon peel oil concentrate

3 kg Zitronenöl mit einem Limonengehalt von 64,1 % wurden mit 1 kg Kieselgel bei Raumtemperatur 90 Minuten lang durch Rüh­ren innig vermischt. Danach wurde das beladene Kieselgel durch Zentrifugation von der flüssigen Phase abgetrennt und in einer Hochdruck-Extraktionsanlage einer Vorextraktion bei 70 bar und 50°C mit 80 kg CO₂ unterworfen. Nach der Entfer­nung der terpenreichen Fraktion aus dem Abscheider wurde bei 280 bar und 50°C die Hauptextraktion durchgeführt, wobei die adsorbierten Aromastoffe mit 40 kg CO₂ aus dem Kieselgel extrahiert wurden.3 kg of lemon oil with a lime content of 64.1% were intimately mixed with 1 kg of silica gel at room temperature for 90 minutes by stirring. Thereafter, the loaded silica gel was separated from the liquid phase by centrifugation and subjected to a pre-extraction at 70 bar and 50 ° C. with 80 kg CO₂ in a high-pressure extraction system. After removing the terpene-rich fraction from the separator, the main extraction was carried out at 280 bar and 50 ° C., the adsorbed aroma substances being extracted from the silica gel with 40 kg of CO₂.

Als Extrakt wurden 30 g Konzentrat mit einem Limonengehalt von 6,7 % erhalten. Der spezifische CO₂-Bedarf betrug insge­samt 40 kg CO₂ pro kg Ausgangsöl.30 g of concentrate with a lime content of 6.7% were obtained as the extract. The specific CO₂ requirement totaled 40 kg CO₂ per kg of starting oil.

Beispiel 2Example 2 Gewinnung von terpenreduziertem Orangen-SchalenölkonzentratExtraction of reduced terpene orange peel oil concentrate

5 kg Orangenöl mit einem Limonengehalt von 95,7 % wurden entsprechend Beispiel 1 mit 1 kg Kieselgel bei Raumtemperatur 120 Minuten lang gerührt. Danach wurde das beladene Kieselgel durch Zentrifugation von der Flüssigphase abgetrennt und in einer Hochdruck-Extraktionsanlage mit 40 kg CO₂ bei 280 bar und 35°C extrahiert. Als Extrakt wurden 625 g Konzentrat mit einem Limonengehalt von 89,6 % erhalten. Der spezifische CO₂-Verbrauch betrug 8 kg CO₂ pro kg Ausgangsöl.5 kg of orange oil with a lime content of 95.7% were stirred according to Example 1 with 1 kg of silica gel at room temperature for 120 minutes. The loaded silica gel was then separated from the liquid phase by centrifugation and extracted in a high-pressure extraction system with 40 kg of CO₂ at 280 bar and 35 ° C. 625 g of concentrate with a lime content of 89.6% were obtained as the extract. The specific CO₂ consumption was 8 kg CO₂ per kg of starting oil.

Beispiel 3Example 3 Gewinnung von terpenreduziertem Zitronen-SchalenölkonzentratExtraction of reduced terpene lemon peel oil concentrate

3 kg Zitronenöl mit einem Limonengehalt von 64,1 % wurden mit 1 kg aktivem Aluminiumoxid bei Raumtemperatur 90 Minuten lang gerührt. Anschließend wurde das beladene Aluminiumoxid durch Zentrifugation von der Flüssigphase abgetrennt und in einer Hochdruck-Extraktionsanlage mit 30 kg CO₂ bei 90 bar und 70°C einer Vorextraktion unterworfen. Nach der Entfernung der abgeschiedenen terpenreichen Fraktion aus dem Abscheider wurde die Hauptextraktion bei 280 bar und 70°C durchgeführt und die adsorbierten Aromastoffe mit 40 kg CO₂ aus dem Alu­miniumoxid extrahiert.3 kg of lemon oil with a lime content of 64.1% was stirred with 1 kg of active aluminum oxide at room temperature for 90 minutes. The loaded aluminum oxide was then separated from the liquid phase by centrifugation and subjected to a pre-extraction in a high-pressure extraction system with 30 kg CO₂ at 90 bar and 70 ° C. After removal of the separated terpene-rich fraction from the separator, the main extraction was carried out at 280 bar and 70 ° C. and the adsorbed aroma substances were extracted from the aluminum oxide with 40 kg CO₂.

Als Extrakt wurden 230 g Konzentrat mit einem Limonengehalt von 41,9 % gewonnen. Der spezifische CO₂-Verbrauch betrug insgesamt 23 kg CO₂ pro kg Ausgangsöl.230 g of concentrate with a lime content of 41.9% were obtained as the extract. The specific CO₂ consumption totaled 23 kg CO₂ per kg of starting oil.

Claims (10)

1. Verfahren zur Entfernung von Terpenen aus etherischen Ölen,
dadurch gekennzeichnet,
daß man a) die terpenhaltigen etherischen Öle mit einem polaren Feststoff (Adsorbens) kontaktiert, b) eine Abtrennung des beladenen Adsorbens von der flüs­sigen, mit Terpenen angereicherten Phase vornimmt und c) das mit etherischem Öl beladene Adsorbens einer Ex­traktion mit verdichtetem CO₂ unterwirft. 1. method for removing terpenes from essential oils,
characterized,
that he a) the terpene-containing essential oils are contacted with a polar solid (adsorbent), b) separates the loaded adsorbent from the liquid phase enriched with terpenes and c) subjecting the adsorbent loaded with essential oil to extraction with compressed CO₂. 2. Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß man als Adsorbens Kieselgel verwendet.2. The method according to claim 1,
characterized,
that one uses silica gel as adsorbent. 3. Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß man als Adsorbens Aluminiumoxid einsetzt.3. The method according to claim 1,
characterized,
that aluminum oxide is used as the adsorbent. 4. Verfahren nach einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet,
daß die Menge des eingesetzten Adsorbens 10 bis 60 Gew.-% bezogen auf die Ausgangsmenge an etherischem Öl beträgt.4. The method according to any one of claims 1 to 3,
characterized,
that the amount of adsorbent used is 10 to 60 wt .-% based on the starting amount of essential oil. 5. Verfahren nach einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet,
daß man die Abtrennung des beladenen Adsorbens von der Flüssigphase durch Zentrifugation durchführt.5. The method according to any one of claims 1 to 4,
characterized,
that one carries out the separation of the loaded adsorbent from the liquid phase by centrifugation. 6. Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet,
daß man das Adsorbens mehrfach einsetzt.6. The method according to any one of claims 1 to 5,
characterized,
that the adsorbent is used several times. 7. Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet,
daß man das Adsorbens mit einer Terpenfraktion aus einem vorangegangenen Schritt kontaktiert, die Mischung in eine Säule füllt und nach Ablassen des Überstandes etherisches Öl durch die Säule hindurchlaufen läßt.7. The method according to any one of claims 1 to 5,
characterized,
that the adsorbent is contacted with a terpene fraction from a previous step, the mixture is filled into a column and, after the supernatant has been drained off, essential oil is passed through the column. 8. Verfahren nach einem der Ansprüche 1 bis 7,
dadurch gekennzeichnet,
daß man die CO₂-Extraktion bei einem Druck von >70 bar, vorzugsweise von 200 bis 300 bar und einer Temperatur von 10 bis 80°C, vorzugsweise von 30 bis 70°C vornimmt.8. The method according to any one of claims 1 to 7,
characterized,
that one carries out the CO₂ extraction at a pressure of> 70 bar, preferably from 200 to 300 bar and a temperature of 10 to 80 ° C, preferably from 30 to 70 ° C. 9. Verfahren nach einem der Ansprüche 1 bis 8,
dadurch gekennzeichnet,
daß man vor der Stufe c) noch eine Vorextraktion mit verdichtetem Kohlendioxid bei einem Druck von <100 bar durchführt.9. The method according to any one of claims 1 to 8,
characterized,
that a pre-extraction with compressed carbon dioxide is carried out at a pressure of <100 bar before stage c). 10. Verfahren nach Anspruch 9,
dadurch gekennzeichnet,
daß die Vorextraktion bei einem Druck von 70 bis 90 bar und einer Temperatur von 30 bis 80°C, vorzugsweise 50 bis 70°C, erfolgt.10. The method according to claim 9,
characterized,
that the pre-extraction takes place at a pressure of 70 to 90 bar and a temperature of 30 to 80 ° C, preferably 50 to 70 ° C.
EP89119001A 1988-10-14 1989-10-12 Process for separating terpenes from essential oils Expired - Lifetime EP0363971B1 (en)

Applications Claiming Priority (2)

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DE3834988A DE3834988A1 (en) 1988-10-14 1988-10-14 METHOD FOR REMOVING TERPENES FROM ETHERIC OILS
DE3834988 1988-10-14

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EP0363971A2 true EP0363971A2 (en) 1990-04-18
EP0363971A3 EP0363971A3 (en) 1991-03-20
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DE (2) DE3834988A1 (en)
ES (1) ES2070877T3 (en)
GR (1) GR3015902T3 (en)
MX (1) MX171557B (en)
RU (1) RU1769761C (en)
ZA (1) ZA897691B (en)

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WO2002036720A1 (en) * 2000-11-06 2002-05-10 Ineos Fluor Holdings Limited Process for reducing the concentration of undesired compounds in a composition
EP1818388A1 (en) 2006-02-10 2007-08-15 Carotech SDN. BHD Process for production of highly enriched fractions of natural compounds from Palm Oil with supercritical and near critical fluids

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US20040058982A1 (en) * 1999-02-17 2004-03-25 Bioavailability System, Llc Pharmaceutical compositions
US6063809A (en) * 1997-08-26 2000-05-16 Bioavailability Systems, Llc Anti-first-pass effect compounds
US6248776B1 (en) * 1997-08-26 2001-06-19 Bioavailability Systems, L.L.C. Anti-first-pass effect compounds
JP2003001002A (en) * 2001-06-18 2003-01-07 Higashimaru Shoyu Co Ltd Extracting method of liquid material
ITMI20031390A1 (en) * 2003-07-08 2005-01-09 Turispharma S R L EXTRACTION METHOD OF ACTIVE MOLECULAR STRUCTURES FROM NATURAL RESINS AND / OR ESSENTIAL OILS.
US7727401B2 (en) 2004-11-09 2010-06-01 Air Products And Chemicals, Inc. Selective purification of mono-terpenes for removal of oxygen containing species
CA2926093C (en) * 2013-10-28 2019-11-12 Totally Natural Solutions Ltd Fractionation of hop oils using liquid and supercritical carbon dioxide.
EP3002327A1 (en) * 2014-10-02 2016-04-06 Sensient Flavors Limited Process for modifying the composition of essential oils
US11078137B1 (en) * 2019-03-08 2021-08-03 Buddies IP Holding, Inc. Sustainable terpene extraction method
CN111363624B (en) * 2020-03-26 2022-06-21 华东理工大学 Method for removing terpene from essential oil

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US7250185B2 (en) 2000-11-06 2007-07-31 Ineos Fluor Holdings Limited Process for reducing the concentration of undesired compounds in a composition
EP1818388A1 (en) 2006-02-10 2007-08-15 Carotech SDN. BHD Process for production of highly enriched fractions of natural compounds from Palm Oil with supercritical and near critical fluids
CN101379174B (en) * 2006-02-10 2013-01-16 卡罗技术有限责任公司 Process for production of highly enriched fractions of natural compounds from palm oil with supercritical and near critical fluids

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ES2070877T3 (en) 1995-06-16
DE3834988A1 (en) 1990-04-19
ZA897691B (en) 1990-07-25
GR3015902T3 (en) 1995-07-31
US5061502A (en) 1991-10-29
DE58909186D1 (en) 1995-05-24
EP0363971B1 (en) 1995-04-19
ATE121447T1 (en) 1995-05-15
JP2541670B2 (en) 1996-10-09
RU1769761C (en) 1992-10-15
EP0363971A3 (en) 1991-03-20
JPH02180997A (en) 1990-07-13

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