WO2009101272A2 - Method for obtaining a dispersion/emulsion of at least one molecule having low water miscibility/solubility - Google Patents

Method for obtaining a dispersion/emulsion of at least one molecule having low water miscibility/solubility Download PDF

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Publication number
WO2009101272A2
WO2009101272A2 PCT/FR2008/001630 FR2008001630W WO2009101272A2 WO 2009101272 A2 WO2009101272 A2 WO 2009101272A2 FR 2008001630 W FR2008001630 W FR 2008001630W WO 2009101272 A2 WO2009101272 A2 WO 2009101272A2
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Prior art keywords
emulsion
water
dispersion
molecule
producing
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PCT/FR2008/001630
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French (fr)
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WO2009101272A3 (en
Inventor
Gabriel Grellier
Hélène HACHET
Agnes Lardet
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Nat'inov
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Publication of WO2009101272A3 publication Critical patent/WO2009101272A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the invention relates to a method for producing a dispersion / emulsion stable in water of at least one molecule soluble or miscible in an organic solvent, more particularly an alcohol such as ethanol or methanol, or the mixture of said solvents with water, but which is poorly soluble / miscible in water.
  • the invention relates in particular to the preparation of emulsion of essential oil in water.
  • Essential oils and some molecules are very weakly soluble / miscible in water. Apart from essential oils of citrus, essential oils are usually obtained by steam stripping. During the condensation of steam, the essential oil spontaneously separates from water, then called hydrosol: this water contains a fraction of the essential essential oil, whose concentration is generally of the order of 0.02% . This solubility is variable, it depends on the composition of the essential oil. When it is desired to incorporate into the water an amount of essential oil greater than its solubility, it is necessary to produce an emulsion.
  • the principle of producing a stable emulsion consists of forming fine droplets dispersed in the continuous phase and preventing the coalescence thereof.
  • the formation of said droplets may be obtained by stirring or passing through a porous membrane using pressure or else by injection under pressure through a valve or an injection nozzle.
  • WO 00/39056 is known, a method which uses opposing jets at high pressure to form microdroplets, the emulsion being then stabilized by an emulsifier.
  • an emulsifier is used.
  • emulsifiers comprise a hydrophobic end and a hydrophilic end.
  • Emulsifiers are surfactants.
  • emulsifiers which are more or less efficient and adapted to the components to be emulsified.
  • the processes used provide nothing microbiologically to the dispersion obtained, except add a sterilization step.
  • a process EP 1470855 is known for creating an emulsion which consists in working in the supercritical state of water, that is to say above 374.2 ° Celsius and at a pressure of at least 218.4. atmospheres. These conditions of temperature and pressure give the water properties such that it becomes a reaction medium, leading to significant alterations of the product introduced into the medium. It is therefore not compatible with essential oils or with other substances that would be degraded.
  • the equipment used to pressurize is complex and expensive given the pressures used.
  • the invention relates to a method for producing an emulsion / dispersion of at least one molecule that is poorly miscible / soluble in water, however soluble / miscible in an organic solvent, characterized in that the molecule (s) by contacting them with water at a temperature of between 100 ° C and 200 ° C under a pressure slightly greater than that required to maintain the water in the liquid phase and to remain under subcritical conditions, for promote the solubilization / miscibility of the molecule or molecules and is cooled prior to return to atmospheric pressure to obtain droplets whose average size is less than one micrometer.
  • FIG 1 an installation for the implementation of the method of producing the emulsion / dispersion.
  • FIG. 2 Droplet size distribution curve for a 0.2% fine lavender essential oil emulsion.
  • FIG. 3 droplet size distribution curve for an emulsion of rosemary essential oil at 1.8% cineole, at 0.3%.
  • the aqueous phase will be the continuous phase and the discontinuous phase will be the hydrophobic phase.
  • essential oils will be used as an example, but other products are suitable insofar as the molecule or molecules are soluble or miscible in certain organic solvents and more particularly in alcohols. Soluble or miscible molecules only in certain highly apolar organic solvents such as hexane (organic solvent) are not suitable.
  • essential oil will include a single oil, a combination of essential oils, or components of an essential oil, alone or in mixtures.
  • the component (s) or molecule (s) are natural, semi-synthetic or synthetic.
  • the molecule is chosen from the following products or their components, alone or as a mixture: essential oils (thyme, orange blossom, etc.), their components
  • the poorly soluble / miscible molecule (s) 3 is introduced by putting them in contact with water 2 at a temperature of between 100.degree.
  • the usable pressure range is 5 to 40 bar.
  • the pressure is always lower than
  • the final concentration of the droplets / particles in the emulsion depends on the molecule and, for example, for the essential oils alone or in mixtures it will be between 0.05% and 1%.
  • the normal pressure condition is atmospheric pressure.
  • the essential oils When the essential oils are introduced at the temperature and pressure conditions indicated above, the essential oils will dissolve in the water and thus distribute themselves evenly in the water. The return to normal conditions will lead to a loss of solubility and therefore the formation of droplets which, because of the homogeneous distribution of molecules in water and the small amount, are then small enough to form a stable emulsion.
  • the droplet size distribution generally ranges from 100 nanometers to one micron.
  • Figure 2 shows the distribution curve for an emulsion of lavender essential oil 0.2% fine.
  • Figure 3 shows the distribution curve for an essential oil emulsion of
  • the introduction is carried out in a continuous mode in a heat exchanger.
  • the introduction of water and essential oil molecules was carried out at a pressure of the order of 5 to 25 bar.
  • Desolvation is obtained by cooling. During this cooling, the solubility / miscibility decreases which causes the formation of fine droplets which result from the fact that the essential oil was uniformly distributed by the effect of forgetting, it is in all respects the solution that will form the droplets.
  • the pressure prevailing in the apparatus can be maintained in the said apparatus by an expansion valve placed at the outlet of the apparatus.
  • the choice of temperature will depend on the molecule (s) of the essential oil, which is otherwise more or less soluble.
  • the emulsification will preferably be carried out at high temperature (160 to 180 ° C.).
  • the emulsification will preferably be prepared at lower temperatures (120-150 ° C.).
  • apolar compound By very strongly apolar compound, include non-oxygenated compounds, for example limonene. Oxygen compounds will generally be less apolar.
  • Essential oils are said to be rich in a compound when said compound is one of the 3 to 4 most concentrated compounds in the essential oil.
  • the working temperature is maintained in a range that best preserves the compound (s).
  • the essential oil becomes less soluble and disperses into fine droplets and forms an emulsion.
  • Emulsifier is not used.
  • the maximum concentration that can be reached is very variable because it depends on the conditions of manufacture of the emulsion and the nature of the compound (s) used, in particular their polarity.
  • the increase in temperature will promote solubility.
  • concentrations not exceeding 0.5% For essential oils rich in highly apolar compounds, it is preferable to work with concentrations not exceeding 0.5%.
  • the process sterilizes the products which is an important point.
  • the solubility / miscibility of naturally poorly soluble / miscible compounds in water is increased by decreasing the polarity of the water.
  • the phases may be previously deoxygenated before introduction into the contacting device, to prevent oxidation phenomena.
  • the gas chosen may be nitrogen N2, helium He or argon Ar.
  • dissolution will be used followed by cooling, the operations being favored by the movement of the fluids such as a turbulent effect produced in a pressurized temperature exchanger 4 (on the order of
  • the pressure of introduction corresponds to the pressure in the apparatus, it is the movement of the fluids and the contribution of heat which contribute to solubilize the essential oils. It is not necessary to resort to large pressures or to high rates of introduction but the introduction rate will be preferentially higher than that producing a laminar flow.
  • a second heat exchanger 5 makes it possible to cool the product. It is at this level that the droplets will form.
  • the dispersion / emulsion will then pass through an expansion valve 6.
  • the two phases can be introduced as a stirred unstable dispersion or the components can be introduced simultaneously by two pumps each having their own flow rate to act as a metering pump.
  • the agitation is obtained by turbulent effect during the continuous introduction with a pump and passage through a heat exchanger.

Abstract

The invention relates to a method for making a stable emulsion/dispersion of a molecule in water, characterised in that said method comprises feeding the molecule(s) (3) by contacting them with water (2) at a temperature of between 100°C and 200°C under a pressure slightly higher than that necessary for maintaining water in a liquid phase in order to enhance the solubilization of the molecule(s), and proceeding with cooling before returning to atmospheric pressure in order to obtain droplets having an average size lower than one micron.

Description

PROCEDE D'OBTENTION D'UNE DISPERSION/EMULSION D'AU MOINS METHOD OF OBTAINING DISPERSION / EMULSION OF AT LEAST
UNE MOLECULE FAIBLEMENT MISCIBLE / SOLUBLE DANS L'EAU.A LOW MISCIBLE MOLECULE / SOLUBLE IN WATER.
L'invention se rapporte à un procédé de réalisation d'une dispersion/émulsion stable dans l'eau d'au moins une molécule soluble ou miscible dans un solvant organique plus particulièrement un alcool tel l'éthanol ou le méthanol, ou le mélange des-dits solvants avec l'eau, mais qui est faiblement soluble/miscible dans l'eau. L'invention se rapporte notamment à la préparation d'émulsion d'huile essentielle dans l'eau.The invention relates to a method for producing a dispersion / emulsion stable in water of at least one molecule soluble or miscible in an organic solvent, more particularly an alcohol such as ethanol or methanol, or the mixture of said solvents with water, but which is poorly soluble / miscible in water. The invention relates in particular to the preparation of emulsion of essential oil in water.
Elle se rapporte également au produit obtenu (émulsion ou dispersion).It also relates to the product obtained (emulsion or dispersion).
Les Huiles essentielles ainsi que certaines molécules sont très faiblement sόlubles/miscibles dans l'eau. Hormis les huiles essentielles de citrus, les huiles essentielles sont généralement obtenues par entraînement à la vapeur d'eau. Lors de la condensation de la vapeur, l'huile essentielle se sépare spontanément de l'eau, alors appelée hydrolat : cette eau contient une fraction de l'huile essentielle soluble, dont la concentration est généralement de l'ordre de 0,02%. Cette solubilité est variable, elle est fonction de la composition de l'huile essentielle. Lorsque l'on souhaite intégrer dans l'eau une quantité d'huile essentielle supérieure à sa solubilité, il est nécessaire de réaliser une émulsion.Essential oils and some molecules are very weakly soluble / miscible in water. Apart from essential oils of citrus, essential oils are usually obtained by steam stripping. During the condensation of steam, the essential oil spontaneously separates from water, then called hydrosol: this water contains a fraction of the essential essential oil, whose concentration is generally of the order of 0.02% . This solubility is variable, it depends on the composition of the essential oil. When it is desired to incorporate into the water an amount of essential oil greater than its solubility, it is necessary to produce an emulsion.
Le principe de réalisation d'une émulsion stable consiste à former de fines gouttelettes dispersées dans la phase continue et à empêcher la coalescence de celles ci.The principle of producing a stable emulsion consists of forming fine droplets dispersed in the continuous phase and preventing the coalescence thereof.
La formation desdites gouttelettes peut être obtenue par agitation ou passage au travers d'une membrane poreuse à l'aide de la pression ou alors par injection sous pression au travers d'un clapet ou d'une buse d'injection.The formation of said droplets may be obtained by stirring or passing through a porous membrane using pressure or else by injection under pressure through a valve or an injection nozzle.
On connait WO 00/39056, un procédé qui utilise des jets opposés à haute pression pour former des microgouttelettes, l' émulsion étant ensuite stabilisée par un émulsifiant.WO 00/39056 is known, a method which uses opposing jets at high pressure to form microdroplets, the emulsion being then stabilized by an emulsifier.
Pour obtenir une émulsion dite stable d'huile dans l'eau ou d'eau dans l'huile, on utilise donc un émulsifiant.To obtain a so-called stable emulsion of oil in water or water in oil, an emulsifier is used.
Ces émulsifiants comprennent une extrémité hydrophobe et une extrémité hydrophile.These emulsifiers comprise a hydrophobic end and a hydrophilic end.
Les émulsifiants sont des agents tensio-actifs.Emulsifiers are surfactants.
Cela permet d'obtenir une phase discontinue dispersée dans une phase continue. En général, c'est uniquement un effet mécanique accompagnant l'action chimique de l'émulsifiant qui va permettre d'obtenir cette dispersion. La quantité d'émulsifiant dépend des produits mis en contact mais également de la proportion relative de ces produits.This makes it possible to obtain a discontinuous phase dispersed in a continuous phase. In general, it is only a mechanical effect accompanying the chemical action of the emulsifier which will make it possible to obtain this dispersion. The amount of emulsifier depends on the products contacted but also on the relative proportion of these products.
On s'intéressera plus particulièrement à une émulsion huile dans l'eau.We will focus more particularly on an oil emulsion in water.
On connaît de nombreux émulsifîants plus ou moins performants et adaptés aux composants à émulsionner.Many emulsifiers are known which are more or less efficient and adapted to the components to be emulsified.
L'inconvénient est la proportion parfois importante d'émulsifiant nécessaire. Il serait préférable de pouvoir supprimer l'émulsifiant. En effet, dans le cas des huiles essentielles, ces émulsifîants piègent sélectivement des composés aromatiques ce qui nécessairement modifie les caractéristiques olfactives. Par ailleurs, la législation est de plus en plus restrictive vis-à-vis des adjuvants utilisés et les consommateurs favorisent les produits sans additifs.The disadvantage is the sometimes important proportion of emulsifier required. It would be better to be able to suppress the emulsifier. Indeed, in the case of essential oils, these emulsifiers selectively trap aromatic compounds which necessarily modifies the olfactory characteristics. In addition, legislation is increasingly restrictive with regard to adjuvants used and consumers favor products without additives.
Les procédés utilisés n'apportent rien sur le plan microbiologique à la dispersion obtenue, sauf ajouter une étape de stérilisation.The processes used provide nothing microbiologically to the dispersion obtained, except add a sterilization step.
Ces procédés ne préviennent généralement pas l'oxydation.These methods generally do not prevent oxidation.
On connaît un procédé EP 1470855 pour créer une émulsion qui consiste à travailler à l'état supercritique de l'eau, c'est-à-dire au dessus de 374,2°Celsius et à une pression d'au moins 218 ,4 atmosphères . Ces conditions de température et pression confèrent à l'eau des propriétés telles qu'elle devient un milieu réactionnel, conduisant à des altérations significatives du produit introduit dans le milieu. Il n'est donc pas compatible avec les huiles essentielles ou avec d'autres substances qui seraient dégradées.A process EP 1470855 is known for creating an emulsion which consists in working in the supercritical state of water, that is to say above 374.2 ° Celsius and at a pressure of at least 218.4. atmospheres. These conditions of temperature and pressure give the water properties such that it becomes a reaction medium, leading to significant alterations of the product introduced into the medium. It is therefore not compatible with essential oils or with other substances that would be degraded.
Le matériel utilisé pour pressuriser est complexe et coûteux compte tenu des pressions utilisées.The equipment used to pressurize is complex and expensive given the pressures used.
On connait un procédé WO 2007/035996 qui décrit un procédé d'émulsification qui prévoit une étape de dégazéîfîcation suivie d'une étape d'agitation nécessaire à la miscibilité. Selon ce procédé, l'étape de dégazéification est nécessaire. La température serait inférieure ou égale à 1000C. L'eau est mélangée avec au moins deux composants. L'invention se propose d'apporter une solution aux problèmes évoqués et notamment de ne pas faire usage d'émulsifiant.There is known a process WO 2007/035996 which describes an emulsification process which provides a degassing step followed by a stirring step necessary for miscibility. According to this method, the degassing step is necessary. The temperature would be less than or equal to 100 ° C. The water is mixed with at least two components. The invention proposes to provide a solution to the problems mentioned and in particular not to make use of emulsifier.
A cet effet, l'invention se rapporte à un procédé de réalisation d'une émulsion/dispersion d'au moins une molécule faiblement miscible/soluble dans l'eau toutefois soluble/miscible dans un solvant organique , caractérisé en ce qu'on introduit la ou les molécules en les mettant en contact avec l'eau à une température comprise entre 100° Celsius et 200° Celsius sous une pression légèrement supérieure à celle nécessaire pour maintenir l'eau en phase liquide et pour rester dans des conditions subcritiques, pour favoriser la solubilisation/ miscibilité de la ou des molécules et on procède à un refroidissement avant retour à la pression atmosphérique pour obtenir des gouttelettes dont la taille moyenne est inférieure au micromètre.For this purpose, the invention relates to a method for producing an emulsion / dispersion of at least one molecule that is poorly miscible / soluble in water, however soluble / miscible in an organic solvent, characterized in that the molecule (s) by contacting them with water at a temperature of between 100 ° C and 200 ° C under a pressure slightly greater than that required to maintain the water in the liquid phase and to remain under subcritical conditions, for promote the solubilization / miscibility of the molecule or molecules and is cooled prior to return to atmospheric pressure to obtain droplets whose average size is less than one micrometer.
L'invention sera bien comprise à l'aide de la description ci après faite à titre d'exemple non limitatif en regard du dessin qui représente schématiquement :The invention will be better understood using the following description given by way of non-limiting example with reference to the drawing which schematically shows:
FIG 1 : une installation pour la mise en œuvre du procédé de réalisation de l' émulsion/dispersion.FIG 1: an installation for the implementation of the method of producing the emulsion / dispersion.
FIG 2 : courbe de répartition de la taille des gouttelettes pour une émulsion d'huile essentielle de lavande fine à 0,2%.FIG. 2: Droplet size distribution curve for a 0.2% fine lavender essential oil emulsion.
FIG 3 : courbe de répartition de la taille des gouttelettes pour une émulsion d'huile essentielle de Romarin à 1,8 cinéole, à 0,3%.FIG. 3: droplet size distribution curve for an emulsion of rosemary essential oil at 1.8% cineole, at 0.3%.
En se reportant au dessin, on voit une installation 1 pour produire une émulsion/dispersion stable dans l'eau d'au moins un composé ( molécule(s)) faiblement soluble/miscible dans l'eau, notamment d'une huile essentielle. La phase aqueuse sera la phase continue et la phase discontinue sera donc la phase hydrophobe.Referring to the drawing, there is shown a plant 1 for producing a stable emulsion / dispersion in water of at least one compound (molecule (s)) poorly soluble / miscible in water, including an essential oil. The aqueous phase will be the continuous phase and the discontinuous phase will be the hydrophobic phase.
On prendra comme exemple les huiles essentielles mais d'autres produits conviennent dans la mesure où la ou les molécules sont toutefois solubles ou miscibles dans certains solvants organiques et plus particulièrement les alcools. Les molécules solubles ou miscibles uniquement dans certains solvants organiques très apolaires tel l'hexane ( solvant organique) ne conviennent pas. Pour la compréhension, par huile essentielle, on comprendra une seule huile, une combinaison d'huiles essentielles, ou des composants d'une huile essentielle, seuls ou en mélanges.The essential oils will be used as an example, but other products are suitable insofar as the molecule or molecules are soluble or miscible in certain organic solvents and more particularly in alcohols. Soluble or miscible molecules only in certain highly apolar organic solvents such as hexane (organic solvent) are not suitable. For understanding, essential oil will include a single oil, a combination of essential oils, or components of an essential oil, alone or in mixtures.
Le ou les composants ou molécules sont naturels, hémi-synthétiques ou synthétiques.The component (s) or molecule (s) are natural, semi-synthetic or synthetic.
La molécule est choisie parmi les produits ou leurs composants seuls ou en mélange suivants : les huiles essentielles (de thym, de fleurs d'oranger, etc),leurs composantsThe molecule is chosen from the following products or their components, alone or as a mixture: essential oils (thyme, orange blossom, etc.), their components
(géraniol etc), des arômes, des parfums, des colorants, des anti-oxydants ( flavonoïde etc ).(geraniol etc), flavors, perfumes, dyes, antioxidants (flavonoid etc).
Selon l'invention, on introduit la ou les molécules faiblement solubles/miscibles 3 en les mettant en contact avec l'eau 2 à une température comprise entre 100° Celsius etAccording to the invention, the poorly soluble / miscible molecule (s) 3 is introduced by putting them in contact with water 2 at a temperature of between 100.degree.
200° Celsius sous une pression légèrement supérieure à celle nécessaire pour maintenir l'eau en phase liquide pour rester dans des conditions subcritiques afin de favoriser la solubilisation/miscibilité de la molécule et on procède à un refroidissement avant retour à la pression atmosphérique pour obtenir des gouttelettes dont la taille moyenne est inférieure au micromètre.200 ° Celsius under a pressure slightly greater than that required to maintain the water in the liquid phase to remain subcritical conditions to promote the solubilization / miscibility of the molecule and is cooled before returning to atmospheric pressure to obtain droplets whose average size is less than one micrometer.
La gamme de pression utilisable est de 5 à 40 bar. La pression est toujours inférieure àThe usable pressure range is 5 to 40 bar. The pressure is always lower than
40 bar.40 bar.
La concentration finale des gouttelettes/particules dans l'émulsion dépend de la molécule et, par exemple, pour les huiles essentielles seules ou en mélanges elle sera comprise entre 0,05% et 1%.The final concentration of the droplets / particles in the emulsion depends on the molecule and, for example, for the essential oils alone or in mixtures it will be between 0.05% and 1%.
Dans ces conditions de température/pression (état de l'eau subcritique), la solubilité/miscibilité de ces molécules telles des huiles essentielles dans l'eau est significativement augmentée par rapport aux conditions normales de température et de pression.Under these conditions of temperature / pressure (state of the subcritical water), the solubility / miscibility of these molecules such as essential oils in the water is significantly increased compared to the normal conditions of temperature and pressure.
La condition de pression normale correspond à la pression atmosphérique.The normal pressure condition is atmospheric pressure.
C'est notamment le passage de l'état soluble à l'état non soluble par changement de pression et de température qui engendre la création de gouttelettes de petites tailles.It is in particular the transition from the soluble state to the non-soluble state by pressure and temperature changes which gives rise to the creation of small size droplets.
Lors de l'introduction des huiles essentielles aux conditions de température et de pression précédemment indiquées, les huiles essentielles vont se solubiliser dans l'eau et donc se répartir uniformément dans l'eau. Le retour aux conditions normales va entraîner une perte de solubilité et donc la formation de gouttelettes qui, du fait de la répartition homogène des molécules dans l'eau et de la petite quantité, sont alors suffisamment petites pour former une émulsion stable.When the essential oils are introduced at the temperature and pressure conditions indicated above, the essential oils will dissolve in the water and thus distribute themselves evenly in the water. The return to normal conditions will lead to a loss of solubility and therefore the formation of droplets which, because of the homogeneous distribution of molecules in water and the small amount, are then small enough to form a stable emulsion.
La répartition de la taille des gouttelettes va généralement de 100 nanomètres à un micron.The droplet size distribution generally ranges from 100 nanometers to one micron.
La figure 2 montre la courbe de répartition pour une émulsion d'huile essentielle de lavande fine à 0,2%.Figure 2 shows the distribution curve for an emulsion of lavender essential oil 0.2% fine.
La figure 3 montre la courbe de répartition pour une émulsion d'huile essentielle deFigure 3 shows the distribution curve for an essential oil emulsion of
Romarin à 1,8 cinéole, à 0,3%.Rosemary with 1.8 cineole, at 0.3%.
Lia petite taille de ces gouttelettes limite les forces qui conduisent à la coalescence.The small size of these droplets limits the forces that lead to coalescence.
L'introduction est réalisée dans un mode continu dans un échangeur de chaleur. iL'introduction de l'eau et des molécules d'huile essentielle a été réalisée à une pression de l'ordre de 5 à 25 Bar.The introduction is carried out in a continuous mode in a heat exchanger. The introduction of water and essential oil molecules was carried out at a pressure of the order of 5 to 25 bar.
La désolvatation est obtenue par refroidissement. Lors de ce refroidissement, la sόlubilitée/miscibilité décroit ce qui entraine la formation de fines gouttelettes qui résultent du fait que l'huile essentielle était uniformément répartie par l'effet de sbliibilisation, c'est en tous points de la solution que vont se former les gouttelettes.Desolvation is obtained by cooling. During this cooling, the solubility / miscibility decreases which causes the formation of fine droplets which result from the fact that the essential oil was uniformly distributed by the effect of forgetting, it is in all respects the solution that will form the droplets.
'La pression régnant dans l'appareil peut être maintenue dans le dit appareil par une vanne de détente placée en sortie d'appareil.The pressure prevailing in the apparatus can be maintained in the said apparatus by an expansion valve placed at the outlet of the apparatus.
Le choix de la température dépendra de la ou les molécules telle de l'huile essentielle qui est par ailleurs plus ou moins soluble.The choice of temperature will depend on the molecule (s) of the essential oil, which is otherwise more or less soluble.
Pour les huiles essentielles riches en composés très fortement apolaires, comme les huiles essentielles d'agrumes, l'émulsification sera réalisée de préférence à haute température (160 à 18O0C). Pour les huiles essentielles contenant des composés moins apolaires. comme l'huile essentielle de menthe poivrée, l'émulsification sera préférentiellement préparée à des températures plus faibles (120-1500C).For essential oils rich in highly highly apolar compounds, such as citrus essential oils, the emulsification will preferably be carried out at high temperature (160 to 180 ° C.). For essential oils containing less apolar compounds. Like the essential oil of peppermint, the emulsification will preferably be prepared at lower temperatures (120-150 ° C.).
Par composé très fortement apolaire, on comprendra notamment les composés non oxygénés, par exemple le limonène. Les composés oxygénés seront généralement moins apolaires.By very strongly apolar compound, include non-oxygenated compounds, for example limonene. Oxygen compounds will generally be less apolar.
Les huiles essentielles sont dites riches en un composé lorsque ledit composé fait partie des 3 à 4 composés les plus concentrés dans l'huile essentielle. La température de travail est maintenue dans une gamme permettant de préserver au mieux le ou les composés.Essential oils are said to be rich in a compound when said compound is one of the 3 to 4 most concentrated compounds in the essential oil. The working temperature is maintained in a range that best preserves the compound (s).
Lorsque le mélange est refroidi, l'huile essentielle devient moins soluble et se disperse en fines gouttelettes et forme une émulsion.When the mixture is cooled, the essential oil becomes less soluble and disperses into fine droplets and forms an emulsion.
C'est notamment la combinaison de l'action physico-chimique par augmentation de la solubilité/miscibilité des composés dans l'eau et le retour vers des conditions de solubilité/miscibilité moindre qui va permettre de constituer cette dispersion stable sans qu'il soit nécessaire d'utiliser un émulsifîant. Cela pour une concentration du ou des huiles essentielles seules ou en mélange supérieure à 0,05% (0,05 gramme d'huile essentielle pour 99,95 grammes d'eau.) et inférieure à 1% (1 gramme d'huile essentielle pour 99 grammes d'eau). La durée de stabilité d'une telle dispersion sera d'au moins six mois à température ambiante (20°C-25°C).It is in particular the combination of the physicochemical action by increasing the solubility / miscibility of the compounds in the water and the return towards conditions of solubility / miscibility that will make it possible to constitute this stable dispersion without it being necessary to use an emulsifier. This is for a concentration of the essential oil (s) alone or in admixture greater than 0.05% (0.05 gram of essential oil for 99.95 grams of water) and less than 1% (1 gram of essential oil). for 99 grams of water). The stability time of such a dispersion will be at least six months at room temperature (20 ° C-25 ° C).
On n'utilise pas d'émulsifiant.Emulsifier is not used.
La concentration maximale qui peut être atteinte est très variable car elle dépend des conditions de fabrication de l' émulsion et de la nature du ou des composés mis en oeuvre, notamment de leur polarité. L'augmentation de température favorisera la solubilité. Pour les huiles essentielles riches en composés très apolaires, on préférera travailler avec des concentrations ne dépassant pas 0,5%.The maximum concentration that can be reached is very variable because it depends on the conditions of manufacture of the emulsion and the nature of the compound (s) used, in particular their polarity. The increase in temperature will promote solubility. For essential oils rich in highly apolar compounds, it is preferable to work with concentrations not exceeding 0.5%.
En fin de procédé, on peut généralement constater qu'une fraction de l'huile essentielle introduite n'est pas émulsionnée car certaines gouttelettes sont trop grosses et coalescent rapidement ; on procédera alors à une séparation, par exemple, par décantation. On peut certes introduire au départ une quantité d'huiles essentielles plus élevée, par exemple 3 à 5%, on obtiendra en final après décantation une teneur finale qui pourra être supérieure à 1% mais l'émulsion sera stable moins longtemps que dans les conditions de fabrications requises.At the end of the process, it can generally be observed that a fraction of the essential oil introduced is not emulsified because certain droplets are too large and coalesce quickly; it will then be separated, for example by decantation. It is possible to introduce a higher quantity of essential oils at the beginning, for example 3 to 5%, a final content which may be greater than 1% will be obtained after final settling, but the emulsion will be stable for less time than under the conditions manufacturing requirements.
Des tests de vieillissement accéléré à 45°C n'ont pas montré de déphasage à trente jours.Accelerated aging tests at 45 ° C showed no phase shift at thirty days.
En travaillant avec une température au delà de 1000C et en dessous de 2000C plusieurs avantages apparaissent.Working with a temperature above 100 0 C and below 200 0 C several advantages appear.
Le procédé stérilise les produits ce qui est un point important. On augmente la solubilité/miscibilité des composés naturellement faiblement solubles/miscibles dans l'eau par diminution de la polarité de l'eau.The process sterilizes the products which is an important point. The solubility / miscibility of naturally poorly soluble / miscible compounds in water is increased by decreasing the polarity of the water.
Avantageusement, les phases pourront être préalablement désoxygénées avant introduction dans le dispositif de mise en contact, afin de prévenir les phénomènes d'oxydation.Advantageously, the phases may be previously deoxygenated before introduction into the contacting device, to prevent oxidation phenomena.
Pour cela, on pourra par exemple désoxygéner préalablement l'une, l'autre ou les 2 phases par dégazage avec un gaz inerte.For this purpose, it will be possible for example to deoxygenate one or the other or the two phases by degassing with an inert gas.
Le gaz choisi pourra être de l'azote N2, de l'hélium He ou de l'argon Ar.The gas chosen may be nitrogen N2, helium He or argon Ar.
Il aura notamment pour effet de désoxygéner les constituants mis en oeuvre et donc réduire l'oxydation lors du procédé mais également après pour la conservation des produits.It will have the effect of deoxygenating the constituents used and thus reduce oxidation during the process but also after the preservation of products.
Pour obtenir de fines gouttelettes, on utilisera la dissolution suivie d'un refroidissement, les opérations étant favorisée par le mouvement des fluides tel un effet turbulent produit dans un échangeur 4 de température sous pression (de l'ordre deTo obtain fine droplets, dissolution will be used followed by cooling, the operations being favored by the movement of the fluids such as a turbulent effect produced in a pressurized temperature exchanger 4 (on the order of
5 à 20 bar) où l'on apporte de l'énergie pour chauffer l'eau et l'huile essentielle. La pression d'introduction correspond à la pression dans l'appareil, c'est le mouvement des fluides et l'apport de chaleur qui contribuent à solubiliser les huiles essentielles. Il n'est pas nécessaire de recourir à des pressions importantes ou à des vitesses d'introduction importantes mais la vitesse d'introduction sera préférentiellement supérieure à celle produisant un flux laminaire.5 to 20 bar) where you bring energy to heat the water and the essential oil. The pressure of introduction corresponds to the pressure in the apparatus, it is the movement of the fluids and the contribution of heat which contribute to solubilize the essential oils. It is not necessary to resort to large pressures or to high rates of introduction but the introduction rate will be preferentially higher than that producing a laminar flow.
Un deuxième échangeur 5 permet de refroidir le produit. C'est à ce niveau que vont se former les gouttelettes.A second heat exchanger 5 makes it possible to cool the product. It is at this level that the droplets will form.
La dispersion/émulsion passera ensuite dans une vanne 6 de détente.The dispersion / emulsion will then pass through an expansion valve 6.
Les deux phases peuvent être introduites sous forme d'une dispersion instable agitée ou alors les composants peuvent être introduits simultanément par deux pompes 10 chacune ayant sont propre débit pour agir comme une pompe doseuse.The two phases can be introduced as a stirred unstable dispersion or the components can be introduced simultaneously by two pumps each having their own flow rate to act as a metering pump.
L'agitation est obtenue par effet turbulent lors de l'introduction en continu avec une pompe et passage dans un échangeur thermique. The agitation is obtained by turbulent effect during the continuous introduction with a pump and passage through a heat exchanger.

Claims

REVENDICATIONS
1. Procédé de réalisation sans émulsifîant d'une émulsion/dispersion stable d'au moins une molécule faiblement soluble/miscible dans l'eau mais toutefois soluble/miscible dans un solvant organique caractérisé en ce qu'on introduit la ou les molécules (3) en les mettant en contact avec l'eau (2) à une température comprise entre 100° Celsius et 200° Celsius sous une pression légèrement supérieure à celle nécessaire pour maintenir l'eau en phase liquide pour favoriser la solubilisation/miscibilité de la ou des molécules et on procède à un refroidissement avant retour à la pression atmosphérique pour obtenir des gouttelettes dont la taille moyenne est inférieure au micromètre.1. Emulsifier-free production process of a stable emulsion / dispersion of at least one weakly soluble / water-miscible molecule but nevertheless soluble / miscible in an organic solvent, characterized in that the molecule (s) is introduced (3). ) by bringing them into contact with the water (2) at a temperature of between 100 ° C and 200 ° C under a pressure slightly greater than that required to maintain the water in the liquid phase to promote the solubilization / miscibility of the molecules and is cooled before returning to atmospheric pressure to obtain droplets whose average size is less than one micrometer.
2. Procédé de réalisation d'une émulsion/dispersion selon la revendication 1 caractérisé en ce que la pression est comprise entre 5 et 40 Bar.2. A method of producing an emulsion / dispersion according to claim 1 characterized in that the pressure is between 5 and 40 bar.
3. Procédé de réalisation d'une émulsion/dispersion selon la revendication 1 ou 2 caractérisé en ce qu'on désoxygène l'eau et/ou la ou les molécules avant mise en contact.3. A method of producing an emulsion / dispersion according to claim 1 or 2 characterized in that deoxygenates the water and / or the molecule or molecules before contacting.
4. Procédé de réalisation d'une émulsion/dispersion selon la revendication 3 caractérisé en ce que pour désoxygéner, on réalise un dégazage avec un gaz inerte.4. A method of producing an emulsion / dispersion according to claim 3 characterized in that to deoxygenate, degassing is carried out with an inert gas.
5. Procédé de réalisation d'une émulsion/dispersion selon la revendication 4 caractérisé en ce que le gaz est choisi parmi l'azote N2, l'hélium He ou l'argon Ar.5. Process for producing an emulsion / dispersion according to claim 4, characterized in that the gas is chosen from nitrogen N2, helium He or argon Ar.
6. Procédé de réalisation d'une émulsion/dispersion selon l'une quelconque des revendications précédentes caractérisé en ce qu'on introduit les deux constituants dans un échangeur de température soit sous forme de dispersion instable soit séparément.6. Process for producing an emulsion / dispersion according to any one of the preceding claims, characterized in that the two constituents are introduced into a temperature exchanger either in the form of an unstable dispersion or separately.
7. Procédé de réalisation d'une émulsion/dispersion selon l'une quelconque des revendications précédentes caractérisé en ce qu'on introduit en continu les composants de l'émulsion/dispersion dans au moins un échangeur thermique.7. Process for producing an emulsion / dispersion according to any one of the preceding claims, characterized in that the components of the emulsion / dispersion are continuously introduced into at least one heat exchanger.
8. Procédé de réalisation d'une émulsion/dispersion selon l'une quelconque des revendications précédentes caractérisé en ce que la molécule est choisie parmi les composants seuls ou en mélange suivants : les huiles essentielles, leurs composants, les parfums, les arômes, les colorants, les anti-oxydants.8. Process for producing an emulsion / dispersion according to any one of the preceding claims, characterized in that the molecule is chosen from the following components alone or as a mixture: essential oils, their components, perfumes, flavors, colorants, antioxidants.
9. Emulsion/ dispersion d'au moins une molécule faiblement soluble/miscible dans l'eau mais toutefois soluble/miscible dans un solvant organique caractérisée en ce qu'elle est obtenue selon le procédé conforme à l'une quelconque des revendications 1 à 8.9. Emulsion / dispersion of at least one molecule slightly soluble / miscible in water but nevertheless soluble / miscible in an organic solvent characterized in that it is obtained according to the method according to any one of claims 1 to 8 .
10. 10.
PCT/FR2008/001630 2007-11-22 2008-11-21 Method for obtaining a dispersion/emulsion of at least one molecule having low water miscibility/solubility WO2009101272A2 (en)

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