EP0363971B1 - Procédé de séparation de terpènes des huiles essentielles - Google Patents

Procédé de séparation de terpènes des huiles essentielles Download PDF

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Publication number
EP0363971B1
EP0363971B1 EP89119001A EP89119001A EP0363971B1 EP 0363971 B1 EP0363971 B1 EP 0363971B1 EP 89119001 A EP89119001 A EP 89119001A EP 89119001 A EP89119001 A EP 89119001A EP 0363971 B1 EP0363971 B1 EP 0363971B1
Authority
EP
European Patent Office
Prior art keywords
adsorbent
process according
terpenes
extraction
essential oils
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89119001A
Other languages
German (de)
English (en)
Other versions
EP0363971A2 (fr
EP0363971A3 (fr
Inventor
Jan Dr. Cully
Erwin Dr. Schütz
Heinz-Rüdiger Dr. Vollbrecht
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
SKW Trostberg AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SKW Trostberg AG filed Critical SKW Trostberg AG
Publication of EP0363971A2 publication Critical patent/EP0363971A2/fr
Publication of EP0363971A3 publication Critical patent/EP0363971A3/fr
Application granted granted Critical
Publication of EP0363971B1 publication Critical patent/EP0363971B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • 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 of the mono- and sesquiterpene series, which have only a limited shelf life and are thermolabile and, moreover, have a lower flavor intensity than the actual flavoring substances, which are predominantly composed of 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.
  • US Pat. No. 4,647,466 discloses a process for the extraction of volatile oxygen-containing substances such as ethyl butyrate or hexanal from citrus oils with the aid of compressed gases, limonene being enriched. Since citrus oils such as Orange oils, however, consisting of up to 95% limonene, require very large amounts of CO2 or long extraction times to carry out the process in order to remove a high proportion of limonene from the aromatic oil with the necessary selectivity.
  • 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 up to 95% terpene content.
  • the adsorbent can be loaded with the essential oil by known methods such as 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 easily 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 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 aroma 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 aroma substances, 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 above the terpene content of the starting oil.
  • this pre-extraction is followed by the main extraction (stage c), in which the oxygen-containing aroma substances are then obtained under gentle conditions.
  • stage c 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. Then the loaded silica gel was separated from the liquid phase by centrifugation and extracted in a high-pressure extraction system with 40 kg 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.

Landscapes

  • 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)
  • Medicines Containing Plant Substances (AREA)
  • Lubricants (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Gas Separation By Absorption (AREA)

Claims (10)

  1. Procédé pour la séparation de terpènes à partir d'huiles essentielles ,
    caractérisé en ce que l'on
    a) met en contact les huiles essentielles contenant du terpène avec une matière solide polaire (agent adsorbant),
    b) on procède à une séparation de l'agent d'adsorbant chargé de la phase liquide enrichie de terpènes et
    c) on soumet l'agent adsorbant chargé d'huile essentielle à une extraction avec du CO₂ condensé.
  2. Procédé selon la revendication 1, caractérisé en ce qu'en tant qu'adsorbant on utilise du gel de silice.
  3. Procédé selon la revendication 1, caractérisé en ce qu'en tant qu'agent adsorbant on utilise de l'oxyde d'aluminium.
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que la quantité de l'agent adsorbant mis en oeuvre est de 10 à 60% en poids rapportés à la quantité de départ d'huile essentielle.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on effectue la séparation de l'agent adsorbant chargé de la phase liquide par centrifugation.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on met en oeuvre l'agent adsorbant plusieurs fois.
  7. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on met en contact l'agent adsorbant avec une fraction de terpènes à partir de l'étape précédente, on charge le mélange dans une colonne et après évacuation du surnageant on fait passer l'huile essentielle dans la colonne.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que l'on procède à l'extraction de CO₂ à une pression > 70 bars, de préférence de 200 à 300 bars et à une température de 10 à 80°C, de préférence de 30 à 70°C.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que l'on effectue avant l'étape c une préextraction supplémentaire avec du dioxyde de carbone condensé à une pression < 100 bars.
  10. Procédé selon la revendication 9, caractérisé en ce que la préextraction s'effectue à une pression de 70 à 90 bars et à une température de 30 à 80°C, de préférence de 50 à 70°C.
EP89119001A 1988-10-14 1989-10-12 Procédé de séparation de terpènes des huiles essentielles Expired - Lifetime EP0363971B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3834988A DE3834988A1 (de) 1988-10-14 1988-10-14 Verfahren zur entfernung von terpenen aus etherischen oelen
DE3834988 1988-10-14

Publications (3)

Publication Number Publication Date
EP0363971A2 EP0363971A2 (fr) 1990-04-18
EP0363971A3 EP0363971A3 (fr) 1991-03-20
EP0363971B1 true EP0363971B1 (fr) 1995-04-19

Family

ID=6365099

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89119001A Expired - Lifetime EP0363971B1 (fr) 1988-10-14 1989-10-12 Procédé de séparation de terpènes des huiles essentielles

Country Status (10)

Country Link
US (1) US5061502A (fr)
EP (1) EP0363971B1 (fr)
JP (1) JP2541670B2 (fr)
AT (1) ATE121447T1 (fr)
DE (2) DE3834988A1 (fr)
ES (1) ES2070877T3 (fr)
GR (1) GR3015902T3 (fr)
MX (1) MX171557B (fr)
RU (1) RU1769761C (fr)
ZA (1) ZA897691B (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124477A (en) * 1996-06-27 2000-09-26 Bioavailability Systems, Llc Anti-first-pass effect compounds
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
US20040058982A1 (en) * 1999-02-17 2004-03-25 Bioavailability System, Llc Pharmaceutical compositions
GB0027047D0 (en) 2000-11-06 2000-12-20 Ici Plc Process for reducing the concentration of undesired compounds in a composition
JP2003001002A (ja) * 2001-06-18 2003-01-07 Higashimaru Shoyu Co Ltd 液状物の抽出方法
ITMI20031390A1 (it) * 2003-07-08 2005-01-09 Turispharma S R L Metodo di estrazione di strutture molecolari attive da resine naturali e/o da oli essenziali.
US7727401B2 (en) * 2004-11-09 2010-06-01 Air Products And Chemicals, Inc. Selective purification of mono-terpenes for removal of oxygen containing species
ATE466065T1 (de) * 2006-02-10 2010-05-15 Carotech Sdn Bhd Verfahren zur gewinnung hochangereicherter naturstoff-fraktionen aus palmöl unter verwendung von superkritischen und beinahe superkritischen flüssigmedien
EP3063260B1 (fr) * 2013-10-28 2019-01-09 Totally Natural Solutions Ltd Fractionnement d'huiles de houblon utilisant du dioxyde de carbone supercritique et liquide
EP3002327A1 (fr) * 2014-10-02 2016-04-06 Sensient Flavors Limited Procédé de modification de la composition d'huiles essentielles
US11078137B1 (en) * 2019-03-08 2021-08-03 Buddies IP Holding, Inc. Sustainable terpene extraction method
CN111363624B (zh) * 2020-03-26 2022-06-21 华东理工大学 一种精油脱萜烯的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2712008A (en) * 1951-06-29 1955-06-28 Justus G Kirchner Production of terpeneless essential oils
US3294550A (en) * 1961-10-12 1966-12-27 Robert M Ikeda Production of full-flavored stable essential oils
US3477856A (en) * 1965-11-10 1969-11-11 Us Agriculture Process for extraction of flavors
US3867262A (en) * 1973-05-21 1975-02-18 Us Agriculture Production of terpeneless essential oils
JPS5410539A (en) * 1977-06-24 1979-01-26 Matsushita Electric Works Ltd Door
JPS59117593A (ja) * 1982-12-24 1984-07-06 長谷川香料株式会社 天然精油の精製方法
JPS6135802A (ja) * 1984-07-27 1986-02-20 Daicel Chem Ind Ltd 有機物の抽出方法
US4647466A (en) * 1985-06-19 1987-03-03 The Procter & Gamble Company Process for the production of citrus flavor and aroma compositions
JPH0664032B2 (ja) * 1985-10-12 1994-08-22 出光石油化学株式会社 超臨界流体による混合物からの特定成分の分離方法
JPS63118399A (ja) * 1986-11-07 1988-05-23 株式会社資生堂 テルペンレス精油

Also Published As

Publication number Publication date
DE58909186D1 (de) 1995-05-24
RU1769761C (en) 1992-10-15
US5061502A (en) 1991-10-29
ES2070877T3 (es) 1995-06-16
EP0363971A2 (fr) 1990-04-18
ZA897691B (en) 1990-07-25
ATE121447T1 (de) 1995-05-15
MX171557B (es) 1993-11-05
DE3834988A1 (de) 1990-04-19
JP2541670B2 (ja) 1996-10-09
EP0363971A3 (fr) 1991-03-20
JPH02180997A (ja) 1990-07-13
GR3015902T3 (en) 1995-07-31

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