EP1307533B1 - Method for fractionating essential oils using at least a fluorinated solvent - Google Patents

Method for fractionating essential oils using at least a fluorinated solvent Download PDF

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EP1307533B1
EP1307533B1 EP01947598A EP01947598A EP1307533B1 EP 1307533 B1 EP1307533 B1 EP 1307533B1 EP 01947598 A EP01947598 A EP 01947598A EP 01947598 A EP01947598 A EP 01947598A EP 1307533 B1 EP1307533 B1 EP 1307533B1
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Prior art keywords
fluorinated
essential oils
phase
essential oil
solvent
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German (de)
French (fr)
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EP1307533A1 (en
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Benoít LEMAIRE
Bernard Mompon
Isabelle Surbled
Michel Surbled
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Extractive
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Extractive
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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
    • C11B9/025—Recovery by solvent extraction

Definitions

  • the invention relates to the field of obtaining essential oils. More specifically, the invention relates to the extraction and fractionation of essential oils of vegetable origin.
  • the invention finds particular application in the fields cosmetics, pharmaceuticals and food.
  • Essential oils are traditionally produced by steaming, hydrodistillation or any other method, variant of the previous ones.
  • the essential oils of citrus constitute a exception, since they can also be produced by pressing bark fruits.
  • FR-A-2 771 408 discloses a process for producing extracts or flower oils.
  • FR-A-1,311 766 A discloses a method of manufacturing perfume concentrates.
  • oils essential may be, for example, to increase the aromatic intensity of the oil essential.
  • the essential oil is subjected to an operation of deterpenation of the separation of terpene hydrocarbons and compounds functionalized whose aromatic notes are more interesting. It can also to eliminate various harmful or toxic constituents.
  • Thujone for example, is a neurotoxic substance present in various essential oils used in food or aromatherapy purposes for example.
  • Psoralens are photosensitizing compounds found in the essential oils of most citrus fruits and more particularly in the essential oil of bergamot. These Compounds must be absolutely eliminated before incorporation of the essential oil in cosmetic compositions.
  • Organic solvents are further affected by various regulations. As an example, the existence of positive lists of solvents concerning food applications. We will also note the regulations relating to the emission of volatile organic compounds (VOCs), which may induce, in brief expiry, important constraints for manufacturers.
  • VOCs volatile organic compounds
  • Supercritical CO 2 treatment has the dual advantage of being a fractionation method without organic solvent and subjecting the feedstock to temperatures lower than those imposed by distillation. On the other hand, it requires specific equipment representing heavy investments.
  • the main objective of the present invention is to propose a method of fractionation of essential oils not presenting the disadvantages of the processes of the state of the art.
  • the invention relates to a method of fractionation of essential oils or fractions of essential oils characterized in that it comprises a step of contacting said oils with an extractant containing at least one fluorinated solvent so as to obtain a fluorinated phase and a non-fluorinated phase and a step of separation of fractions of essential oils contained in said fluorinated phase and in said non-fluorinated phase.
  • the process described makes it possible to satisfy the requirements techniques of various treatments applied to essential oils or fractions of essential oils, both at laboratory and production scale industrial.
  • the applications of the proposed method we find in particular the deterpenation of essential oils or the removal of certain harmful or toxic.
  • the perfluorinated solvents more particularly concerned by the present invention are perfluoro N-methylmorpholine (also known commercially under the name PF5052), n-perfluoropentane (PF5050), n-perfluorohexane (PF5060), n-perfluoroheptane (PF5070) and n-perfluorooctane (PF5080) and their isomers.
  • PF5052 perfluoro N-methylmorpholine
  • PF505050 n-perfluoropentane
  • PF5060 n-perfluorohexane
  • PF5070 n-perfluoroheptane
  • PF5080 n-perfluorooctane
  • hydrofluoroethers more particularly concerned by the present invention are methoxynonafluorobutane (C 4 F 9 -O-CH 3 ), also called HFE7100, and ethoxynonafluorobutane (C 4 F 9 -OC 2 H 5 ), also called HFE7200, and their isomers.
  • the phase containing the fluorinated solvent is enriched mainly in monoterpene hydrocarbons and, to a lesser extent, in sesquiterpene hydrocarbons.
  • the non solubilized by fluorinated solvents is mainly enriched in functionalized constituents with protic functions (alcohols, phenols) and in a measurement of functionalized compounds with non-protic functions (esters, ethers, aldehydes, ketones ).
  • the constituents of the fluorinated phase can be recovered by evaporation of the extractant, preferably under reduced pressure in order to reduce the temperature of the treatment.
  • the non-fluorinated phase which contains only a small amount of extractant, can be treated the same way.
  • the non-fluorinated phase may, where appropriate, be cooled to cause demixing or precipitation of the constituents less soluble. These can then be easily recovered and desolventized.
  • the fluorinated phase may also be treated by cooling as indicated above.
  • fractionation can be carried out in batch mode, in semi-continuous mode or in continuous mode. If the solubility of hydrocarbons in a given fluorinated solvent is considered too low, the semi-continuous mode will be preferred. He will have the advantage, for example, of meeting productivity requirements when implementation of the process in an industrial setting.
  • the essential oil is kept in an enclosure whose temperature is set at a considered value as optimal for extraction.
  • the fluorinated solvent distributed in the form of droplets, passes through the layer of essential oil from below upward under the effect of difference in density of the two liquid phases.
  • the fluorinated phase loaded with extract, is collected at the bottom of the extraction stage and then directed to a floor of separation of the extractant and the extracted constituents by distillation. The extractant thus regenerated is recycled to the extraction stage.
  • the temperature of the extractant from the recycling stage can then be brought to this same value, by passing the extractant in an exchanger before distribution in the charge to be treated.
  • This example is intended to quantify the partition coefficient of the main tracers of clove essential oil between a fluorinated solvent and the oil essential itself.
  • the fluorinated solvents tested are perfluorohexane (PF5060), perfluorooctane (PF5080) and perfluoro N-methylmorpholine (PF5052).
  • oil essential clove was chosen because of its high eugenol content, compound comprising a free phenolic hydroxyl and a phenolic hydroxyl engaged in an ether link.
  • the fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent.
  • the mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.
  • Table 2 specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium.
  • the table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
  • the fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent.
  • the mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.
  • Table 4 specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium.
  • the table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
  • This example is intended to quantify the partition coefficient of the main tracers of the essential oil of oregano between a fluorinated solvent and the essential oil herself.
  • the fluorinated solvents tested are perfluorohexane (PF5060), perfluorooctane (PF5080) and perfluoro N-methylmorpholine (PF5052).
  • oil Oregano essential oil was chosen for its high content of carvacrol, comprising a free phenolic hydroxyl.
  • the fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent.
  • the mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.
  • Table 6 specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium.
  • the table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
  • the extraction is carried out in a liquid / liquid extractor operating in semi-continuously.
  • the extraction stage containing the essential oil is equipped with a jacket powered by a thermostatic fluid.
  • the extraction stage is fed PF5060 (perfluorohexane) from the recycling stage and distributed in the form of droplets in the layer of essential oil.
  • PF5060 perfluorohexane
  • the fluorinated phase, charged in extract is sent back to the boiler of the recycling stage by a system overflow.
  • the flow rate of recycled fluorinated solvent is set by adjusting the power of boiler heating.
  • Table 7 indicates the mass content of the main tracers of the original essential oil of oregano, the raffinate at the end of treatment and the extract obtained.
  • main tracers chemical family % in the initial oil % in raffinate % in the excerpt ⁇ -thujene monoterpène 1.1 0.3 4.2 ⁇ -terpinene 1.0 0.3 3.4 ⁇ -myrcene 2.3 0.7 7.8 ⁇ -terpinene 4.1 1.0 14.8 p -cymene 13.0 4.0 42.8 ⁇ -caryophyllene sesquiterpène 3.1 0.7 11.0 linalool monoterpene alcohol 2.1 2.6 0.4 carvacrol single OH phenol free and sterically hindered 67.1 86.0 5.3
  • the raffinate obtained is thus enriched to 86% in carvacrol against 67% in the oil starting point by extraction of 80% terpene hydrocarbons.

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

Abstract

The invention concerns a method for fractinating essential oils or essential oil fractions, characterised in that it comprises a step which consists in contacting said essential oils with an extracting agent containing at least a fluorinated solvent so as to obtain a fluorinated phase and a non-fluorinated phase and a step which consists in separating the essential oils contained in said fluorinated phase and in said non-fluorinated phase.

Description

L'invention concerne le domaine de l'obtention des huiles essentielles. Plus précisément, l'invention concerne l'extraction et du fractionnement des huiles essentielles d'origine végétales.The invention relates to the field of obtaining essential oils. More specifically, the invention relates to the extraction and fractionation of essential oils of vegetable origin.

L'invention trouve notamment son application dans les domaines cosmétiques, pharmaceutiques et alimentaires.The invention finds particular application in the fields cosmetics, pharmaceuticals and food.

Les huiles essentielles sont, de façon classique, produites par entraínement à la vapeur, par hydrodistillation ou par toute autre méthode, variante des précédentes. Les huiles essentielles d'agrumes constituent une exception puisqu'elles peuvent également être produites par pressage des écorces des fruits.Essential oils are traditionally produced by steaming, hydrodistillation or any other method, variant of the previous ones. The essential oils of citrus constitute a exception, since they can also be produced by pressing bark fruits.

Les constituants des huiles essentielles peuvent être classés en fonction de leur degré de fonctionnalisation et en fonction de la nature des fonctions chimiques qu'ils portent. On distingue ainsi les hydrocarbures non fonctionnalisés qui sont le plus souvent des hydrocarbures monoterpéniques et des hydrocarbures sesquiterpéniques. Les fonctions chimiques les plus courantes, substituant les squelettes hydrocarbonés des constituants des huiles essentielles sont :

  • la fonction aldéhyde (ex : citral, benzaldéhyde)
  • la fonction cétone (ex : pulégone, carvone)
  • la fonction ester ou lactone (ex : acétate de lynalyle, tridécanolide)
  • la fonction éther ( ex : eucalyptol, anéthol)
  • la fonction hydroxyle (ex : citronellol, menthol), qualifiée de phénolique lorsqu'elle substitue un motif hydrocarboné aromatique (ex : thymol, eugénol)
The constituents of essential oils can be classified according to their degree of functionalization and according to the nature of the chemical functions they carry. The nonfunctionalised hydrocarbons that are most often monoterpene hydrocarbons and sesquiterpene hydrocarbons are thus distinguished. The most common chemical functions, substituting the hydrocarbon skeletons of the constituents of essential oils are:
  • the aldehyde function (ex: citral, benzaldehyde)
  • the ketone function (eg pulegone, carvone)
  • the ester or lactone function (eg lynalyl acetate, tridecanolide)
  • the ether function (eg eucalyptol, anethole)
  • the hydroxyl function (eg citronellol, menthol), qualified as phenolic when it substitutes an aromatic hydrocarbon unit (eg thymol, eugenol)

Il est souvent nécessaire de fractionner les huiles essentielles, c'est-à-dire de séparer les différentes fractions qui les constituent. FR-A-2 771 408 divulgue un procédé de production d'extraits ou d'huiles de fleurs. FR-A-1 311 766 A divulgue un procédé de fabrication de concentrés de parfumerie.It is often necessary to split the essential oils, that is to say separate the different fractions that constitute them. FR-A-2 771 408 discloses a process for producing extracts or flower oils. FR-A-1,311 766 A discloses a method of manufacturing perfume concentrates.

Ainsi, certaines applications exigent des qualités particulières d'huiles essentielles. Il peut s'agir, par exemple, d'augmenter l'intensité aromatique de l'huile essentielle. Dans ce cas, l'huile essentielle est soumise à une opération de déterpénation consistant à séparer les hydrocarbures terpéniques et les composés fonctionnalisés dont les notes aromatiques sont plus intéressantes. Il peut également s'agir d'éliminer divers constituants nocifs ou toxiques. La thujone, par exemple est une substance neurotoxique présente dans diverses huiles essentielles utilisées à des fins alimentaires ou aromathérapiques par exemple. Les psoralènes sont des composés photosensibilisants présents dans les huiles essentielles de la plupart des agrumes et plus particulièrement dans l'huile essentielle de bergamote. Ces composés doivent être absolument éliminés avant incorporation de l'huile essentielle dans des compositions cosmétiques.Thus, certain applications require particular qualities of oils essential. It may be, for example, to increase the aromatic intensity of the oil essential. In this case, the essential oil is subjected to an operation of deterpenation of the separation of terpene hydrocarbons and compounds functionalized whose aromatic notes are more interesting. It can also to eliminate various harmful or toxic constituents. Thujone, for example, is a neurotoxic substance present in various essential oils used in food or aromatherapy purposes for example. Psoralens are photosensitizing compounds found in the essential oils of most citrus fruits and more particularly in the essential oil of bergamot. These Compounds must be absolutely eliminated before incorporation of the essential oil in cosmetic compositions.

Les procédés les plus couramment employés pour le fractionnement des huiles essentielles sont la distillation, l'adsorption-désorption ou le traitement par CO2 supercritique.The most commonly used methods for the fractionation of essential oils are distillation, adsorption-desorption or supercritical CO 2 treatment.

L'un des inconvénients de la distillation est qu'elle soumet les constituants les plus labiles à des températures suffisamment élevées pour conduire à des réactions de dégradation. Dans le cas de l'adsorption-désorption, ce sont l'utilisation des solvants organiques, la faible productivité et le coût du procédé qui constituent les principaux inconvénients.One of the disadvantages of distillation is that it subjects the constituents more labile at temperatures high enough to lead to reactions degradation. In the case of adsorption-desorption, it is the use of organic solvents, the low productivity and the cost of the process that make up the main disadvantages.

Les solvants organiques sont en outre concernés par diverses réglementations. A titre d'exemple, on retiendra l'existence de listes positives de solvants concernant des applications alimentaires. On retiendra également la réglementation relative à l'émission de composés organiques volatils (COV), qui risque d'induire, à brève échéance, des contraintes importantes pour les industriels.Organic solvents are further affected by various regulations. As an example, the existence of positive lists of solvents concerning food applications. We will also note the regulations relating to the emission of volatile organic compounds (VOCs), which may induce, in brief expiry, important constraints for manufacturers.

Ces contraintes réglementaires proviennent du caractère soit nocif soit toxique des solvants organiques utilisés. Cette nocivité et cette toxicité se manifestent à des teneurs généralement faibles en solvants résiduels dans les extraits obtenus. Afin de supprimer les risques sanitaires, il est donc nécessaire de mettre en oeuvre des procédés de désolvantisation qui présentent plusieurs inconvénients. En effet, outre le surcoût qu'ils induisent, ces procédés de désolvantisation peuvent avoir, selon les conditions opératoires appliquées, une incidence négative sur la qualité des extraits produits.These regulatory constraints come from either harmful or toxic nature organic solvents used. This harmfulness and this toxicity are manifested generally low levels of residual solvents in the extracts obtained. In order to to eliminate health risks, it is therefore necessary to implement desolventization processes which have several disadvantages. Indeed, besides the additional cost they induce, these desolventization processes may have, according to the operating conditions applied, a negative impact on the quality of the extracts products.

Le traitement au CO2 supercritique offre le double avantage d'être une méthode de fractionnement sans solvant organique et de soumettre la charge à des températures inférieures à celles imposées par la distillation. En revanche, il requiert des équipements spécifiques représentant des investissements lourds.Supercritical CO 2 treatment has the dual advantage of being a fractionation method without organic solvent and subjecting the feedstock to temperatures lower than those imposed by distillation. On the other hand, it requires specific equipment representing heavy investments.

L'objectif principal de la présente invention est de proposer un procédé de fractionnement d'huiles essentielles ne présentant pas les inconvénients des procédés de l'état de la technique.The main objective of the present invention is to propose a method of fractionation of essential oils not presenting the disadvantages of the processes of the state of the art.

Cet objectif est atteint grâce à l'invention qui concerne un procédé de fractionnement d'huiles essentielles ou de fractions d'huiles essentielles caractérisé en ce qu'il comprend une étape consistant à mettre en contact lesdites huiles essentielles avec un extractant contenant au moins un solvant fluoré de façon à obtenir une phase fluorée et une phase non fluorée et une étape de séparation des fractions d'huiles essentielles contenues dans ladite phase fluorée et dans ladite phase non fluorée.This objective is achieved thanks to the invention which relates to a method of fractionation of essential oils or fractions of essential oils characterized in that it comprises a step of contacting said oils with an extractant containing at least one fluorinated solvent so as to obtain a fluorinated phase and a non-fluorinated phase and a step of separation of fractions of essential oils contained in said fluorinated phase and in said non-fluorinated phase.

Selon la matière première mise en oeuvre, les conditions opératoires appliquées et les solvants fluorés utilisés, le procédé décrit permet de satisfaire aux exigences techniques de divers traitements appliqués aux huiles essentielles ou fractions d'huiles essentielles, tant à l'échelle du laboratoire qu'à l'échelle de la production industrielle. Parmi les applications du procédé proposé, on trouve notamment la déterpénation d'huiles essentielles ou l'élimination de certains composés nocifs ou toxiques.Depending on the raw material used, the operating conditions applied and the fluorinated solvents used, the process described makes it possible to satisfy the requirements techniques of various treatments applied to essential oils or fractions of essential oils, both at laboratory and production scale industrial. Among the applications of the proposed method, we find in particular the deterpenation of essential oils or the removal of certain harmful or toxic.

Selon l'invention, ces solvants fluorés peuvent être préférentiellement :

  • des perfluoroalcanes aliphatiques caractérisés par la formule générale CnF2n+2 (5≤n≤15)
  • des perfluoroalcanes possédant un motif cyclique et caractérisés par la formule générale CnF2n (5≤n≤15)
  • des perfluoroalcanes possédant deux motifs cycliques et caractérisés par la formule générale CnF2n-2 (8≤n≤15)
  • la perfluoro N-méthylmorpholine de formule générale C5ONF11
  • des hydrofluoroéthers (HFE) caractérisés par la formule générale CnF2n+1OCmH2m+1 où 3≤n≤8 et 1≤m≤6
According to the invention, these fluorinated solvents may be preferentially:
  • aliphatic perfluoroalkanes characterized by the general formula C n F 2n + 2 (5≤n≤15)
  • perfluoroalkanes having a cyclic unit and characterized by the general formula C n F 2n (5≤n≤15)
  • perfluoroalkanes having two cyclic units and characterized by the general formula C n F 2n-2 (8≤n≤15)
  • perfluoro N-methylmorpholine of general formula C 5 ONF 11
  • hydrofluoroethers (HFE) characterized by the general formula C n F 2n + 1 OC m H 2m + 1 where 3≤n≤8 and 1≤m≤6

Les solvants perfluorés plus particulièrement concernés par la présente invention sont la perfluoro N-méthylmorpholine (également connu dans le commerce sous la dénomination PF5052), les n-perfluoropentane (PF5050) , n-perfluorohexane (PF5060), n-perfluoroheptane (PF5070) et n-perfluorooctane (PF5080) ainsi que leurs isomères. Les hydrofluoroéthers plus particulièrement concernés par la présente invention sont le méthoxynonafluorobutane (C4F9-O-CH3), également appelé HFE7100, et l'éthoxynonafluorobutane (C4F9-O-C2H5), également appelé HFE7200, ainsi que leurs isomères.The perfluorinated solvents more particularly concerned by the present invention are perfluoro N-methylmorpholine (also known commercially under the name PF5052), n-perfluoropentane (PF5050), n-perfluorohexane (PF5060), n-perfluoroheptane (PF5070) and n-perfluorooctane (PF5080) and their isomers. The hydrofluoroethers more particularly concerned by the present invention are methoxynonafluorobutane (C 4 F 9 -O-CH 3 ), also called HFE7100, and ethoxynonafluorobutane (C 4 F 9 -OC 2 H 5 ), also called HFE7200, and their isomers.

Par rapport aux solvants traditionnels d'extraction, les solvants fluorés précités bénéficient de nombreux avantages :

  • ils sont ininflammables et n'imposent pas, de ce fait, l'utilisation d'équipements particuliers de production et de protection. Cette caractéristique est particulièrement intéressante dans des perspectives de production à l'échelle industrielle puisqu'elle a une incidence directe sur le coût des produits finis ;
  • ils ne présentent pas de risque pour l'écosystème et sont en conformité avec les réglementations environnementales les plus strictes. Ils ne sont pas inscrits à la liste des composés organiques volatils (COV), leur potentiel de destruction de la couche d'ozone est nul et leur contribution à l'effet de serre est très faible ;
  • ils sont chimiquement inertes, inodores, incolores et sans saveur. Ils n'ont donc aucune incidence négative sur les propriétés des extraits ou des formulations qui les contiennent ou qu'ils ont servi à préparer ;
  • même à fortes doses, ils sont atoxiques par inhalation, adsorption ou contact répétés. Cette absence de toxicité a d'ailleurs été mise à profit pour incorporer les HFE dans des formules cosmétiques (demandes de brevet WO 99/26594 et WO 99/26600) ;
  • ils ont une capacité calorifique et une chaleur latente de vaporisation faibles comparativement à celles des solvants organiques couramment utilisés en extraction. Les coûts énergétiques de mise en oeuvre et de retraitement sont donc notablement allégés ;
  • ils ont des tensions de vapeurs élevées qui facilitent la désolvantisation des extraits .
Un autre avantage réside dans leur sélectivité exceptionnelle, particulièrement dans le cas des solvants perfluorés. Le demandeur a en effet constaté qu'ils solubilisent les hydrocarbures préférentiellement aux dérivés fonctionnalisés. Parmi les dérivés fonctionnalisés, il a également été observé que les dérivés à fonctions non protiques (éther, ester, cétone, aldéhyde...) sont, de façon générale, solubilisés préférentiellement aux dérivés à fonctions protiques (alcools, phénols) et que parmi les dérivés à fonctions hydroxyles libres, les alcools sont solubilisés préférentiellement aux phénols. Il a encore été observé que parmi les hydrocarbures, les monoterpènes sont solubilisés préférentiellement aux sesquiterpènes.Compared to traditional extraction solvents, the aforementioned fluorinated solvents have many advantages:
  • they are non-flammable and therefore do not impose the use of special production and protection equipment. This feature is particularly interesting in industrial scale production prospects since it has a direct impact on the cost of finished products;
  • they pose no risk to the ecosystem and are in compliance with the strictest environmental regulations. They are not included in the list of volatile organic compounds (VOCs), their potential for destruction of the ozone layer is zero and their contribution to the greenhouse effect is very low;
  • they are chemically inert, odorless, colorless and tasteless. They therefore have no negative impact on the properties of extracts or formulations that contain them or that they were used to prepare;
  • even in high doses, they are non-toxic by inhalation, adsorption or repeated contact. This lack of toxicity has also been used to incorporate HFE in cosmetic formulas (patent applications WO 99/26594 and WO 99/26600);
  • they have a low heat capacity and latent heat of vaporization compared to those of the organic solvents commonly used in extraction. The energy costs of implementation and reprocessing are therefore significantly reduced;
  • they have high vapor tensions which facilitate the desolvation of the extracts.
Another advantage lies in their exceptional selectivity, particularly in the case of perfluorinated solvents. The applicant has indeed found that they solubilize hydrocarbons preferentially functionalized derivatives. Among the functionalized derivatives, it has also been observed that the derivatives with non-protic functions (ether, ester, ketone, aldehyde, etc.) are, in general, solubilized preferentially with the derivatives with protic functions (alcohols, phenols) and that among derivatives with free hydroxyl functions, the alcohols are solubilized preferentially with phenols. It has also been observed that among hydrocarbons, monoterpenes are solubilized preferentially to sesquiterpenes.

Selon l'invention, en mettant en contact une huile essentielle et un extractant contenant au moins un solvant fluoré, il est ainsi possible d'obtenir deux phases dont les compositions dépendront notamment de l'huile essentielle traitée, des solvants fluorés utilisés et de la température de traitement.According to the invention, by bringing into contact an essential oil and an extractant containing at least one fluorinated solvent, it is thus possible to obtain two phases of which the compositions will depend in particular on the treated essential oil, on the solvents used fluoride and treatment temperature.

En règle générale, la phase contenant le solvant fluoré est enrichie principalement en hydrocarbures monoterpéniques et, dans une moindre mesure, en hydrocarbures sesquiterpéniques. Egalement en règle générale, la phase non solubilisée par les solvants fluorés (phase non fluorée) est principalement enrichie en constituants fonctionnalisés à fonctions protiques (alcools, phénols) et dans une moindre mesure en composés fonctionnalisés à fonctions non protiques (esters, éthers, aldéhydes, cétones ...).As a general rule, the phase containing the fluorinated solvent is enriched mainly in monoterpene hydrocarbons and, to a lesser extent, in sesquiterpene hydrocarbons. Also as a general rule, the non solubilized by fluorinated solvents (non-fluorinated phase) is mainly enriched in functionalized constituents with protic functions (alcohols, phenols) and in a measurement of functionalized compounds with non-protic functions (esters, ethers, aldehydes, ketones ...).

Les constituants de la phase fluorée peuvent être récupérés par évaporation de l'extractant, de préférence sous pression réduite afin de réduire la température de traitement. La phase non fluorée, qui ne contient qu'une faible quantité d'extractant, peut être traitée de la même façon. La phase non fluorée peut, le cas échéant, être refroidie afin de provoquer une démixtion ou une précipitation des constituants les moins solubles. Ces derniers peuvent alors être facilement récupérés et désolvantisés. Le cas échéant, la phase fluorée peut également être traitée par refroidissement comme indiqué ci-dessus.The constituents of the fluorinated phase can be recovered by evaporation of the extractant, preferably under reduced pressure in order to reduce the temperature of the treatment. The non-fluorinated phase, which contains only a small amount of extractant, can be treated the same way. The non-fluorinated phase may, where appropriate, be cooled to cause demixing or precipitation of the constituents less soluble. These can then be easily recovered and desolventized. Where appropriate, the fluorinated phase may also be treated by cooling as indicated above.

On notera que le fractionnement peut être effectué en mode discontinu, en mode semi-continu ou en mode continu. Si la solubilité des hydrocarbures dans un solvant fluoré donné est jugée trop faible, le mode semi-continu sera préféré. Il aura l'avantage, par exemple, de satisfaire aux exigences de productivité lors d'une mise en oeuvre du procédé dans un cadre industriel. It should be noted that the fractionation can be carried out in batch mode, in semi-continuous mode or in continuous mode. If the solubility of hydrocarbons in a given fluorinated solvent is considered too low, the semi-continuous mode will be preferred. He will have the advantage, for example, of meeting productivity requirements when implementation of the process in an industrial setting.

Dans le cas d'une mise en oeuvre en mode semi-continu, l'huile essentielle est maintenue dans une enceinte dont la température est fixée à une valeur considérée comme optimale pour l'extraction. Le solvant fluoré, distribué sous forme de gouttelettes, traverse la couche d'huile essentielle de bas en haut sous l'effet de la différence de densité des deux phases liquides. La phase fluorée, chargée en extrait, est collectée en bas de l'étage d'extraction et dirigée ensuite vers un étage de séparation de l'extractant et des constituants extraits, par distillation. L'extractant ainsi régénéré est recyclé en direction de l'étage d'extraction.In the case of an implementation in semi-continuous mode, the essential oil is kept in an enclosure whose temperature is set at a considered value as optimal for extraction. The fluorinated solvent, distributed in the form of droplets, passes through the layer of essential oil from below upward under the effect of difference in density of the two liquid phases. The fluorinated phase, loaded with extract, is collected at the bottom of the extraction stage and then directed to a floor of separation of the extractant and the extracted constituents by distillation. The extractant thus regenerated is recycled to the extraction stage.

Selon les nécessités, diverses améliorations peuvent être apportées au procédé. Il est possible, en particulier, d'inerter au préalable l'extractant en le soumettant à tout procédé de dégazage (barbotage par un gaz inerte, ébullition à reflux, sonication, dégazage sur membrane...). Cette opération d'inertage réduit la teneur en oxygène dissous, ordinairement élevée dans les solvants fluorés et limite ainsi les risques de dégradation des composés les plus oxydables, tels que les aldéhydes. On peut également, durant l'opération de fractionnement, maintenir une atmosphère inerte, statique ou dynamique, dans l'enceinte d'extraction.As needed, various improvements can be made to the process. It is possible, in particular, to inerter beforehand the extractant by submitting it to any degassing process (bubbling with an inert gas, boiling under reflux, sonication, membrane degassing ...). This inerting operation reduces the content of dissolved oxygen, which is usually high in fluorinated solvents and thus limits risks of degradation of the most oxidizable compounds, such as aldehydes. We can also, during the fractionation operation, maintain an atmosphere inert, static or dynamic, in the extraction chamber.

Si la température d'extraction doit être maintenue à une valeur optimale précise, la température de l'extractant provenant de l'étage de recyclage peut alors être amenée à cette même valeur, par passage de l'extractant dans un échangeur thermique avant sa distribution dans la charge à traiter.If the extraction temperature must be kept at an optimum value precise, the temperature of the extractant from the recycling stage can then be brought to this same value, by passing the extractant in an exchanger before distribution in the charge to be treated.

Afin d'augmenter les débits d'extractant ou de réduire la température d'ébullition de l'extrait dans l'étage de recyclage, il est possible de mettre en oeuvre le procédé à une pression inférieure à la pression atmosphérique. Il est alors nécessaire d'équiper le condenseur de l'étage de recyclage d'un système de réfrigération ayant une puissance suffisante pour limiter les pertes en extractant.To increase extractant flow or reduce temperature of boiling of the extract in the recycling stage, it is possible to implement the process at a pressure below atmospheric pressure. It is then necessary to equip the condenser of the recycling stage of a refrigeration system having sufficient power to limit the losses of extractant.

Afin d'ajuster la sélectivité requise pour le fractionnement à effectuer, il est possible d'ajouter à l'extractant fluoré un co-solvant constitué d'au moins un solvant organique. On préfèrera cependant utiliser un extractant constitué uniquement de solvants fluorés pour les avantages cités plus haut.In order to adjust the selectivity required for the fractionation to be carried out, it is possible to add to the fluorinated extractant a co-solvent consisting of at least one solvent organic. However, it is preferable to use an extractant consisting solely of fluorinated solvents for the advantages mentioned above.

Les exemples décrits ci-dessous illustrent quelques possibilités d'applications de la présente invention. Ils concernent les huiles essentielles de clou de girofle, de bergamote et d'origan. Ces exemples ne sont pas limitatifs. En effet, le fractionnement d'huiles essentielles par solvants fluorés peut être appliqué à de nombreuses autres huiles essentielles, pour des utilisations à des fins notamment cosmétiques, pharmaceutiques ou alimentaires.The examples described below illustrate some possible applications of the present invention. They concern the essential oils of clove, bergamot and oregano. These examples are not limiting. Indeed, the fractionation of essential oils by fluorinated solvents may be applied to many other essential oils, for particular uses cosmetics, pharmaceuticals or food.

Exemple 1 - Fractionnement d'huile essentielle de clou de girofleExample 1 - Splitting of clove essential oil

Cet exemple est destiné à quantifier le coefficient de partage des principaux traceurs de l'huile essentielle de clou de girofle entre un solvant fluoré et l'huile essentielle elle-même. Les solvants fluorés testés sont le perfluorohexane (PF5060), le perfluorooctane (PF5080) et la perfluoro N-méthylmorpholine (PF5052). L'huile essentielle de clou de girofle a été choisie en raison de sa richesse en eugénol, composé comprenant un hydroxyle phénolique libre et un hydroxyle phénolique engagé dans une liaison éther.This example is intended to quantify the partition coefficient of the main tracers of clove essential oil between a fluorinated solvent and the oil essential itself. The fluorinated solvents tested are perfluorohexane (PF5060), perfluorooctane (PF5080) and perfluoro N-methylmorpholine (PF5052). oil essential clove was chosen because of its high eugenol content, compound comprising a free phenolic hydroxyl and a phenolic hydroxyl engaged in an ether link.

Le fractionnement de 100 g d'huile essentielle est effectué avec 100 g de solvant fluoré. Le mélange est agité pendant 20 minutes à 25°C. Après décantation, les deux phases liquides sont volumées et analysées par chromatographie en phase gazeuse.The fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent. The mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.

Le tableau 1 ci-dessous précise pour chaque solvant fluoré testé :

  • le volume initial d'huile essentielle (Vi HE)
  • le volume initial de solvant fluoré (Vi SF)
  • le volume de l'huile essentielle surnageante à l'équilibre (Veq HE)
  • le volume de la phase fluorée à l'équilibre (Veq SF)
Figure 00080001
Table 1 below specifies for each fluorinated solvent tested:
  • the initial volume of essential oil (Vi HE)
  • the initial volume of fluorinated solvent (Vi SF)
  • the volume of the supernatant equilibrium essential oil (Veq HE)
  • the volume of the equilibrium fluoride phase (Veq SF)
Figure 00080001

Le tableau 2 ci-dessous précise, pour chaque solvant fluoré testé, le coefficient de partage (Keq), entre les deux phases à l'équilibre, des principaux traceurs de l'huile essentielle ; K est défini comme le rapport des concentrations de chaque traceur dans la phase fluorée et dans l'huile essentielle surnageante lorsque le système biphasique est à l'équilibre. Le tableau précise en outre, pour chaque traceur, sa teneur initiale dans l'huile essentielle (Ci) ainsi que sa famille chimique d'appartenance ou sa fonctionnalisation.

Figure 00090001
Table 2 below specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium. The table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
Figure 00090001

Ces résultats indiquent que les solvants fluorés utilisés sont sélectifs et qu'ils solubilisent les espèces hydrocarbonées préférentiellement aux phénols à fonctions hydroxyles libres ou bloquées. Le fait que l'humulène ne soit pas détecté dans la phase fluorée et dû, d'une part, à sa faible teneur initiale dans l'huile essentielle et, d'autre part, à un autre aspect de la sélectivité des solvants fluorés qui se manifeste entre hydrocarbures monoterpéniques et sesquiterpéniques.These results indicate that the fluorinated solvents used are selective and that they solubilize the hydrocarbon species preferentially to phenols with functions free or blocked hydroxyls. The fact that humulene is not detected in the fluorinated phase and due, on the one hand, to its low initial content in the essential oil and, on the other hand, to another aspect of the selectivity of fluorinated between monoterpene and sesquiterpene hydrocarbons.

Exemple 2 - Fractionnement d'huile essentielle de bergamoteExample 2 - Fractionation of essential oil of bergamot

Cet exemple est destiné à quantifier le coefficient de partage des principaux traceurs de l'huile essentielle de bergamote entre un solvant fluoré et l'huile essentielle elle-même. Les solvants fluorés testés sont le perfluorohexane (PF5060), le perfluorooctane (PF5080) et la perfluoro N-méthylmorpholine (PF5052). L'huile essentielle de bergamote a été choisie pour les raisons suivantes :

  • sa richesse en linalol, composé comprenant un hydroxyle non phénolique
  • sa teneur élevée en psoralènes (composés photosensibilisants de la famille des coumarines)
  • la présence de flavonoïdes due au mode de production par pressage de l'huile essentielle ; ces flavonoïdes sont fortement fonctionnalisés et portent des fonctions phénoliques dont certaines peuvent être glycosylées, estérifiées ou éthérifiées
This example is intended to quantify the partition coefficient of the main tracers of the essential oil of bergamot between a fluorinated solvent and the essential oil itself. The fluorinated solvents tested are perfluorohexane (PF5060), perfluorooctane (PF5080) and perfluoro N-methylmorpholine (PF5052). The essential oil of bergamot was chosen for the following reasons:
  • its richness in linalool, compound comprising a non-phenolic hydroxyl
  • its high content of psoralens (photosensitizing compounds of the coumarin family)
  • the presence of flavonoids due to the production mode by pressing the essential oil; these flavonoids are highly functionalized and carry phenolic functions, some of which may be glycosylated, esterified or etherified

Le fractionnement de 100 g d'huile essentielle est effectué avec 100 g de solvant fluoré. Le mélange est agité pendant 20 minutes à 25°C. Après décantation, les deux phases liquides sont volumées et analysées par chromatographie en phase gazeuse.The fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent. The mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.

Le tableau 3 ci-dessous précise pour chaque solvant fluoré testé :

  • le volume initial d'huile essentielle (Vi HE)
  • le volume initial de solvant fluoré (Vi SF)
  • le volume de l'huile essentielle surnageante à l'équilibre (Veq HE)
  • le volume de la phase fluorée à l'équilibre (Veq SF)
Figure 00100001
Table 3 below specifies for each fluorinated solvent tested:
  • the initial volume of essential oil (Vi HE)
  • the initial volume of fluorinated solvent (Vi SF)
  • the volume of the supernatant equilibrium essential oil (Veq HE)
  • the volume of the equilibrium fluoride phase (Veq SF)
Figure 00100001

Le tableau 4 ci-dessous précise, pour chaque solvant fluoré testé, le coefficient de partage (Keq), entre les deux phases à l'équilibre, des principaux traceurs de l'huile essentielle ; K est défini comme le rapport des concentrations de chaque traceur dans la phase fluorée et dans l'huile essentielle surnageante lorsque le système biphasique est à l'équilibre. Le tableau précise en outre, pour chaque traceur, sa teneur initiale dans l'huile essentielle (Ci) ainsi que sa famille chimique d'appartenance ou sa fonctionnalisation.

Figure 00110001
Table 4 below specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium. The table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
Figure 00110001

Ces résultats indiquent que les solvants fluorés utilisés sont sélectifs et qu'ils solubilisent les espèces hydrocarbonées préférentiellement aux espèces à fonctions hydroxyles libres non phénoliques. On notera en particulier que le linalol n'est pas détecté en dépit d'une teneur pourtant non négligeable dans l'huile essentielle (14%). La sélectivité vis-à-vis de l'acétate de lynalyle est en revanche moins marquée que dans le cas du linalol et traduit le caractère moins polaire des esters. On notera cependant que le coefficient de partage de l'acétate de lynalyle reste significativement inférieur à ceux des hydrocarbures terpéniques.These results indicate that the fluorinated solvents used are selective and that they solubilize the hydrocarbon species preferentially to the species with functions non-phenolic free hydroxyls. It should be noted in particular that linalool is not detected despite a nonetheless significant content in the essential oil (14%). The selectivity towards lynalyl acetate is on the other hand less marked than in the case of linalool and reflects the less polar nature of the esters. We will note however, the partition coefficient of lynalyl acetate remains significantly lower than terpene hydrocarbons.

Exemple 3 - Fractionnement d'huile essentielle d'origanExample 3 - Fractionation of essential oil of oregano

Cet exemple est destiné à quantifier le coefficient de partage des principaux traceurs de l'huile essentielle d'origan entre un solvant fluoré et l'huile essentielle elle-même. Les solvants fluorés testés sont le perfluorohexane (PF5060) , le perfluorooctane (PF5080) et la perfluoro N-méthylmorpholine (PF5052). L'huile essentielle d'origan a été choisie pour sa teneur élevée en carvacrol, composé comprenant un hydroxyle phénolique libre. This example is intended to quantify the partition coefficient of the main tracers of the essential oil of oregano between a fluorinated solvent and the essential oil herself. The fluorinated solvents tested are perfluorohexane (PF5060), perfluorooctane (PF5080) and perfluoro N-methylmorpholine (PF5052). oil Oregano essential oil was chosen for its high content of carvacrol, comprising a free phenolic hydroxyl.

Le fractionnement de 100 g d'huile essentielle est effectué avec 100 g de solvant fluoré. Le mélange est agité pendant 20 minutes à 25°C. Après décantation, les deux phases liquides sont volumées et analysées par chromatographie en phase gazeuse.The fractionation of 100 g of essential oil is carried out with 100 g of fluorinated solvent. The mixture is stirred for 20 minutes at 25 ° C. After settling, the two liquid phases are volumized and analyzed by chromatography in phase gas.

Le tableau 5 ci-dessous précise pour chaque solvant fluoré testé :

  • le volume initial d'huile essentielle (Vi HE)
  • le volume initial de solvant fluoré (Vi SF)
  • le volume de l'huile essentielle surnageante à l'équilibre (Veq HE)
  • le volume de la phase fluorée à l'équilibre (Veq SF)
Figure 00120001
Table 5 below specifies for each fluorinated solvent tested:
  • the initial volume of essential oil (Vi HE)
  • the initial volume of fluorinated solvent (Vi SF)
  • the volume of the supernatant equilibrium essential oil (Veq HE)
  • the volume of the equilibrium fluoride phase (Veq SF)
Figure 00120001

Le tableau 6 ci-dessous précise, pour chaque solvant fluoré testé, le coefficient de partage (Keq), entre les deux phases à l'équilibre, des principaux traceurs de l'huile essentielle ; K est défini comme le rapport des concentrations de chaque traceur dans la phase fluorée et dans l'huile essentielle surnageante lorsque le système biphasique est à l'équilibre. Le tableau précise en outre, pour chaque traceur, sa teneur initiale dans l'huile essentielle (Ci) ainsi que sa famille chimique d'appartenance ou sa fonctionnalisation.

Figure 00130001
Table 6 below specifies, for each fluorinated solvent tested, the partition coefficient (K eq ), between the two phases at equilibrium, of the main tracers of the essential oil; K is defined as the ratio of the concentrations of each tracer in the fluorinated phase and in the supernatant essential oil when the biphasic system is at equilibrium. The table further specifies, for each tracer, its initial content in the essential oil (C i ) and its chemical family of membership or functionalization.
Figure 00130001

Ces résultats indiquent que les solvants fluorés utilisés sont sélectifs et que, de façon générale, ils solubilisent les espèces hydrocarbonées terpéniques préférentiellement aux espèces à fonctions hydroxyles libres. On notera en particulier que le carvacrol n'est que très faiblement représenté dans la phase fluorée alors qu'il est le constituant largement majoritaire (70%) de l'huile essentielle.These results indicate that the fluorinated solvents used are selective and that In general, they solubilize the terpenic hydrocarbon species preferentially to species with free hydroxyl functions. We will note in particular that carvacrol is only very weakly represented in the fluorinated phase while it is the major constituent (70%) of the essential oil.

Dans le cas du traitement par le PF5052, le linalol constitue une exception avec une distribution dans la phase fluorée plus élevée que celles de la grande majorité des hydrocarbures.In the case of treatment with PF5052, linalool is an exception with a distribution in the fluorinated phase higher than those of the large majority of hydrocarbons.

Exemple 4 - Fractionnement d'huile essentielle d'origan en mode semi-continuExample 4 - Fractionation of oregano essential oil in semi-continuous mode

Le fractionnement de l'huile essentielle d'origan en mode semi-continu a été effectué avec le perfluorohexane (PF5060) dont la température d'ébullition à pression atmosphérique est de 56°C.The fractionation of Oregano essential oil in semi-continuous mode has been performed with perfluorohexane (PF5060) whose boiling point at atmospheric pressure is 56 ° C.

L'extraction est effectuée dans un extracteur liquide/liquide fonctionnant en semi-continu. L'étage d'extraction contenant l'huile essentielle est équipé d'une jaquette alimentée par un fluide de thermostatisation. L'étage d'extraction est alimenté en PF5060 (perfluorohexane) provenant de l'étage de recyclage et distribué sous forme de gouttelettes dans la couche d'huile essentielle. La phase fluorée, chargée en extrait, est renvoyée au bouilleur de l'étage de recyclage par un système de trop-plein. Le débit de solvant fluoré recyclé est fixé en ajustant la puissance de chauffage du bouilleur.The extraction is carried out in a liquid / liquid extractor operating in semi-continuously. The extraction stage containing the essential oil is equipped with a jacket powered by a thermostatic fluid. The extraction stage is fed PF5060 (perfluorohexane) from the recycling stage and distributed in the form of droplets in the layer of essential oil. The fluorinated phase, charged in extract, is sent back to the boiler of the recycling stage by a system overflow. The flow rate of recycled fluorinated solvent is set by adjusting the power of boiler heating.

40.5 g d'huile essentielle d'origan ont été traités de cette façon, à 20°C et par un volume total de 7.2 litres (12.2 kg) de perfluorohexane. En fin d'extraction, le raffinat et l'extrait sont désolvantisés et analysés par chromatographie en phase gazeuse.40.5 g of oregano essential oil were treated in this way at 20 ° C and by a total volume of 7.2 liters (12.2 kg) of perfluorohexane. At the end of extraction, the raffinate and the extract are desolventized and analyzed by chromatography in phase gas.

Le tableau 7 ci-dessous indique la teneur massique en principaux traceurs de l'huile essentielle d'origan initiale, du raffinat en fin de traitement et de l'extrait obtenu. principaux traceurs famille chimique % dans l'huile initiale % dans le raffinat % dans l'extrait α-thujène monoterpène 1.1 0.3 4.2 α-terpinène 1.0 0.3 3.4 β-myrcène 2.3 0.7 7.8 γ-terpinène 4.1 1.0 14.8 p-cymène 13.0 4.0 42.8 β-caryophyllène sesquiterpène 3.1 0.7 11.0 linalol alcool monoterpénique 2.1 2.6 0.4 carvacrol phénol à OH unique libre et stériquement encombré 67.1 86.0 5.3 Table 7 below indicates the mass content of the main tracers of the original essential oil of oregano, the raffinate at the end of treatment and the extract obtained. main tracers chemical family % in the initial oil % in raffinate % in the excerpt α-thujene monoterpène 1.1 0.3 4.2 α-terpinene 1.0 0.3 3.4 β-myrcene 2.3 0.7 7.8 γ-terpinene 4.1 1.0 14.8 p -cymene 13.0 4.0 42.8 β-caryophyllene sesquiterpène 3.1 0.7 11.0 linalool monoterpene alcohol 2.1 2.6 0.4 carvacrol single OH phenol free and sterically hindered 67.1 86.0 5.3

Le bilan massique pour chaque famille de molécule et pour chacune des fractions récupérées est résumé dans le tableau 8 ci-dessous. famille chimique masse dans l'huile initiale (g) masse dans le raffinat (g) masse dans l'extrait (g) monoterpènes / sesquiterpènes 9.9 1.9 5.25 alcool monoterpénique 0.8 0.7 0.02 phénol à OH unique libre et stériquement encombré 27 24 0.33 The mass balance for each molecule family and for each of the fractions recovered is summarized in Table 8 below. chemical family mass in the initial oil (g) mass in the raffinate (g) mass in the extract (g) monoterpenes / sesquiterpenes 9.9 1.9 5.25 monoterpene alcohol 0.8 0.7 0.02 single OH phenol free and sterically hindered 27 24 0.33

Ces résultats indiquent que le traitement par le perfluorohexane extrait majoritairement des monoterpènes et des sesquiterpènes non fonctionnalisés, et augmente ainsi la teneur en composé aromatique dans le raffinat.These results indicate that treatment with perfluorohexane extract mostly monoterpenes and non-functionalized sesquiterpenes, and thus increases the content of aromatic compound in the raffinate.

Le raffinat obtenu est donc enrichi à 86% en carvacrol contre 67% dans l'huile essentielle de départ par extraction de 80 % des hydrocarbures terpéniques.The raffinate obtained is thus enriched to 86% in carvacrol against 67% in the oil starting point by extraction of 80% terpene hydrocarbons.

Claims (11)

  1. A method for fractionating essential oils or fractions of essential oils, characterized in that it comprises a step consisting of contacting said essential oils with an extracting agent containing at least one fluorinated solvent in order to obtain a fluorinated phase and a non-fluorinated phase and a step for separating the fractions of essential oils contained in said fluorinated phase and in said non-fluorinated phase, and in that said fluorinated solvent is selected from:
    aliphatic perfluoroalkanes with general formula CnF2n+2 with 5 ≤ n ≤ 15;
    perfluoroalkanes having a cyclic unit, with general formula CnF2n with 5 ≤ n ≤ 15;
    perfluoroalkanes having two cyclic units, with general formula CnF2n-2 with 8 ≤ n ≤ 15; or is
    perfluoro-N-methylmorpholine with formula C5ONF11.
  2. The method according to claim 1, characterized in that said extracting agent comprises at least one organic co-solvent.
  3. The method according to any of claims 1 or 2, characterized in that it is conducted in at least one heated and thermostatized enclosure at a pre-determined temperature.
  4. The method according to any of claims 1 to 3, characterized in that said separation step is carried out by evaporation.
  5. The method according to claim 4, characterized in that said evaporation is carried under reduced pressure.
  6. The method according to any of claims 1 to 5, characterized in that it comprises a recycling step of said fluorinated solvent.
  7. The method according to claims 3 and 6, characterized in that said recycled fluorinated solvent is brought to said predetermined temperature.
  8. The method according to any of claims 3 to 7, characterized in that said liquid phase and/or said non-fluorinated phase are cooled before proceeding with the separation of the fraction(s) of essential oils which they contain.
  9. The method according to any of claims 1 to 8, characterized in that it comprises a step for desolventizing the obtained fractions of essential oils.
  10. The method according to any of claims 1 to 9, characterized in that it comprises a step consisting of inertizing said fluorinated solvent.
  11. The method according to any of claims 1 to 10, characterized in that it consists of placing said essential oil in a heated and thermostatized enclosure, distributing said extracting agent containing said fluorinated solvent as droplets in the essential oil, collecting said fluorinated phase in the lower portion of said enclosure.
EP01947598A 2000-06-22 2001-06-22 Method for fractionating essential oils using at least a fluorinated solvent Expired - Lifetime EP1307533B1 (en)

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ATE287938T1 (en) 2005-02-15
FR2810672A1 (en) 2001-12-28
DE60108643D1 (en) 2005-03-03
FR2810672B1 (en) 2003-11-07
US20040026318A1 (en) 2004-02-12
AU2001269249A1 (en) 2002-01-02
WO2001098443A1 (en) 2001-12-27

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