EP4142676A1

EP4142676A1 - Method for extracting odour from a plant material, in particular from mute flowers, in solid form

Info

Publication number: EP4142676A1
Application number: EP21732401.1A
Authority: EP
Inventors: Guillaume Gillet; Isabelle Desjardins-Lavisse
Original assignee: Genialis Biotech SAS
Current assignee: Genialis Biotech SAS
Priority date: 2020-04-29
Filing date: 2021-04-29
Publication date: 2023-03-08
Also published as: CA3176032A1; US20230174891A1; WO2021219963A1; FR3109731B1; FR3109731A1

Abstract

The invention relates to the field of natural odours and fragrances. More particularly, the invention relates to a method for extracting odour from a plant material and to the provision thereof in solid form. This method combines steps of extraction, gas dissolution, cryogenics, or even freeze-drying. The odour thus captured in the form of a deep-frozen matrix or of dehydrated powder can be used as a natural perfuming ingredient, in particular in cosmetics. The invention relates very particularly to the obtaining of perfuming extracts derived from mute flowers.

Description

PROCESS FOR EXTRACTING ODOR FROM A PLANT MATERIAL, IN PARTICULAR FROM MUTE FLOWERS, IN SOLID FORM

The invention relates to the field of natural odors and perfumes. More particularly, the invention relates to a process for extracting an odor from a plant material and its provision in solid form. This process combines steps of extraction, gas dissolution, cryogenics, or even lyophilization. The odor thus captured in the form of a frozen matrix or of a dehydrated powder can be used as a natural perfuming ingredient, in particular in cosmetics. The invention relates very particularly to the production of perfume extracts derived from mute flowers.

Field of the invention

With the exception of rose, jasmine, tuberose, magnolia, narcissus, daffodil, mimosa, cassia, orange blossom, lavender, broom, ylang- ylang and osmanthus, all other flowers are said to be “mute”. A flower is said to be "mute" when it is not possible, by the conventional extraction techniques of steam distillation or extraction with volatile solvents, or even of effleurage, to obtain an extract. usable in perfumery because the extraction yields are too low, or even harmful. For example, if tuberose can be found in the form of an absolute, its price is very high, in the order of € 5,000 per kg, intended exclusively for exceptional perfumes.

Since the second half of the 19th century, chemists have proposed solutions to try to compensate for this lack, by isolating and identifying compounds likely to allow the re-composition of the scents expected by the play of their combination, without ever allowing to faithfully reproduce the scents. subtle natural scents given off by mute flowers.

Furthermore, it can be noted that research to develop new extraction techniques or improve existing techniques is very active. The patent databases reveal, for example, nearly 4,000 applications over the years 2018 and 2019 alone. These are essentially proposals for optimizing known processes, by choosing more suitable solvents or combinations of solvents and more. natural for example, by optimizing the treatment parameters for given pairs of compounds / raw material, or even by selecting more favorably the extraction of a particular compound. Few new extraction techniques have emerged in recent years, offering no alternative to the problem of mute flowers in particular.

On the other hand, natural scent extracts are usually extracted in liquid form. The conservation of these preparations is delicate because the molecules constituting them are unstable, the odors being able to change according to the temperature, the exposure to light ... which poses problems of conservation, storage and transport. There is a real need for a more efficient and less expensive process for preparing natural fragrant ingredients from plant material in stabilized forms that can be used industrially. In particular, there is no method capable of extracting odors from dumb flowers.

Prior art

Patent FR3011848A1 describes a process for obtaining an oily plant extract from plant material comprising the steps of: a) mixing said raw material with at least one fatty substance; b) heating said mixture by microwave at a power of 0.1 to 5 watts per gram of mixture to a temperature of 25 ° C to 60 ° C; and c) recovering the fatty substance which forms after mixing and heating the oily extract.

Patent FR3081684A1 describes a process for obtaining a product in the form of frozen granules, particles or balls rich in dissolved gas and associated equipment from a liquid, semi-liquid or pasty matrix comprising the steps of gasifying the matrix by incorporation of a gas, in dispensing the matrix in the form of drops and cryogenizing the matrix drops by immersion in a cryogenic fluid, characterized in that the step of gasification of the matrix consists in dissolving a large quantity of the gas generated by evaporation of the cryogenic fluid in the matrix drops by increasing the number of gas molecules in a zone of high gas density, called a zone of high molecular density, located above the surface of the cryogenic fluid and on the trajectory of drops of matrix before their immersion in the fluid, said zone of high molecular density being created by carrying out the gasification and cryogenization of the gasified drops within a closed enclosure arranged to allow evacuation of the gas generated by the evaporation of the cryogenic fluid by natural convection.

Disclosure of the invention

The inventors have developed a process making it possible to extract an odor from a plant material and to preserve it in solid form, either frozen or in the form of a dehydrated powder. Remarkably, it extracts the smells of mute flowers.

This extraction process comprises the following steps: a) Disposing of a plant material b) Carrying out a treatment of said plant material, optionally under an inert atmosphere, in order to have a product in the form of a liquid matrix, semi- liquid or pasty c) dissolving a gas in said matrix by passing through a zone dense in gas molecules, such a density being obtained (i) either by a flow of gas generated by the evaporation of a cryogenic fluid, (ii ) or by an increase in pressure; d) Cryogenizing said gas-rich matrix obtained in step c) under pressure and temperature conditions making it possible to maintain said gas in said matrix to obtain frozen granules, particles or beads.

The frozen granules, particles or beads can be lyophilized so as to obtain an odorous extract in the form of a dehydrated powder.

Advantages of the invention

The present invention has many advantages with regard to the state of the art.

The proposed extraction process is simple, fast and inexpensive. It uses two technologies known to those skilled in the art, namely cryogenics and lyophilization.

The first step is a step of freezing or deep freezing by cryogenics. In order to preserve the integrity of the plant matrix, the method involves first of all the dissolution of a gas in the matrix before cryogenics, then carrying out the cryogenics step under pressure so as to maintain throughout the process the gas trapped in the matrix and in particular in the frozen granules, particles or beads. The presence of the gas, in particular when it is an inert gas, protects the odorous matrix during freezing and allows substantial improvements both in the properties of the products obtained and in the drying by freeze-drying.

The second step is a freeze-drying step. Lyophilization is a process of dehydration by sublimation of water under conditions of temperature and pressure allowing the water contained in solid form in the products to be transformed directly into water vapor for elimination. It makes it possible to obtain dehydrated products in powder form, the odorous properties of which are maintained.

The extraction process according to the invention has the advantage of being rapid. Cryogenics is an almost instantaneous process, making it possible to continuously produce and at high rates (several hundred kg per hour on standard equipment) balls of initially fluid product. The time saving is considerable compared to freezing in a cold room, even if they operate at very low temperatures (-40 ° C to -80 ° C in general). The cryogenized beads are extracted from the materials producing them at temperatures generally between -80 ° C and -120 ° C, which makes it possible to start freeze-drying directly, with products whose temperature is around - 60 ° C, without a prior step of cooling. More surprisingly, the lyophilization time itself is very greatly reduced (down to a factor of at least 2).

With regard to the product obtained, the combination of gas dissolution with cryogenics makes it possible to obtain frozen products containing a large amount of gas. When this gas is not oxygen, oxidation reactions are avoided. In addition, the lyophilization of such products makes it possible to eliminate the major part of the water contained in the product. The quality of the dehydrated products is higher than that of the lyophilized products obtained by a conventional process because the conditions set implemented in this process are on the whole softer, less aggressive and less destructuring for the matrix. These properties, odorous in particular, are therefore better preserved.

Unexpectedly, it is possible to obtain powders with a good extraction yield starting from a plant material without adding a support. Such a powder which is 100% derived from vegetable matter is of high quality. However, depending on the plant species, it may be necessary to add a support, either because the extraction leads to an oily product which is unsuitable for being shaped in powder form, or to fix certain odorous molecules and thus increase the yield. The addition of support is also useful for the standardization of commercial powders.

The frozen granules, particles or beads as well as the lyophilized powder obtained at the end of the process contain the odorous molecules extracted from the biological material and the odorous ingredient is of high quality. The inventors have in fact observed that the odor contained in these solid ingredients faithfully reproduces the odor of fresh plant material and that this odor lasts for a very long time without deteriorating. In addition, these fragrant ingredients do not contain alcohol and therefore make it possible to formulate perfumes without alcohol. The fragrant ingredients therefore have significantly improved properties compared to the extracts available hitherto.

Remarkably, the method of the invention makes it possible to extract the odors from mute flowers. This result is extremely interesting and opens new horizons in the world of perfumery which can now access the complex scents of mute flowers thanks to natural ingredients of high olfactory quality at acceptable costs.

These fragrant ingredients - 100% natural - will also be able to be integrated into natural perfumes until now deprived of the aromas of mute flowers, since they are only available via combinations of synthetic molecules. It's a safe bet that these ingredients will revolutionize this booming sector.

From the point of view of the user, in particular perfume manufacturers, the formulation of perfuming compositions from odorous ingredients offered in the form of dehydrated powder is also advantageous. It provides ease of use, dosage and storage and the shelf life is long due to the stability of the product. The use can in particular be facilitated by a formulation of the powder in a compressed form (compact powder), offered for example in a format of small pebbles of a determined weight, or of granules.

Another advantage of the dehydrated powders according to the invention is that they dissolve quickly and leave no deposit, which allows them to be easily introduced into liquid perfume compositions.

Thus, the inventors have developed a new process for preparing extracts of natural plant matrices offering a high quality olfactory rendering and yields allowing the industrial use of the ingredients obtained. DETAILED DESCRIPTION OF THE INVENTION

A first object of the invention relates to a process for preparing an odorous ingredient in solid form from a plant material comprising the steps of: a) disposing of a plant material b) carrying out a mechanical treatment of the raw material , optionally under an inert atmosphere, in order to have a product in the form of a liquid, semi-liquid or pasty matrix c) Dissolving a gas in said matrix by passing through a zone dense in gas molecules, such a density being obtained (i) either by a flow of gas generated by the evaporation of a cryogenic fluid, (ii) or by an increase in pressure; d) Cryogenizing said gas-rich matrix obtained in step c) under pressure and temperature conditions making it possible to maintain said trapped gas in order to obtain frozen granules, particles or beads.

In an advantageous embodiment, the method further comprising the steps of: a) Lyophilization of said granules, particles or beads; b) Obtaining said odorous ingredient in the form of a dehydrated powder.

The dissolved gas can be an inert gas such as nitrogen, argon ... or a non-inert gas such as CO 2 or nitrous oxide, or a mixture of gases. When it is desired to protect the matrix against oxidation, a particularly preferred cryogenic fluid is liquid nitrogen.

By the terms “under pressure” within the meaning of the invention, is meant conditions which allow the dissolution and / or trapping of a gas in a matrix and / or its maintenance in said matrix during deep freezing. Pressurization can be obtained either by increasing the pressure or by bringing the matrix into contact with a cryogenic fluid, the evaporation of this gas creating a gas molecule density equivalent to pressurization so that the gas molecules dissolve in the matrix.

When the dense zone of molecules is obtained by increasing the pressure, this pressure is greater than atmospheric pressure, and may in particular be greater than 0.5 bar, 1 bar, 2 bars, 5 bars, 10 bars, 50 bars, 100 bars, 200 bars, or even 250 bars or more. In a particular embodiment, it is between 2 and 100 bars. For the sake of clarity, it is specified that the pressures expressed in this document correspond to relative pressures, that is to say that atmospheric pressure is considered as a pressure of 0 bar.

In a preferred embodiment, the zone dense in gas molecules is obtained at least in part by virtue of a flow of gas generated by the evaporation of a cryogenic fluid. It can be obtained by combining the evaporation of a cryogenic fluid with an increase in pressure. The terms "a gas flow generated by the evaporation of a cryogenic fluid" cover the flow resulting directly from the evaporation of a cryogenic fluid as well as any controlled flow (direction, flow rate, etc.), by injection gas or by suction for example, which allows the creation of one or more exchange zones between the matrix and a large number of gas molecules.

The pressure and temperature conditions applied in step d) must make it possible to maintain the gas trapped in the matrix in step c). Those skilled in the art will know how to adjust the pressure and temperature conditions during step d), so that the solubility of the gas in the matrix is greater than or equal to that used during step c). Said solubility is in particular influenced by the temperature (for gases it increases when the temperature decreases) and by the pressure (balance of the partial pressures between the matrix and the gas).

Thus, steps c) and d) take place under correlated conditions (between these two steps) in order to allow the gas to dissolve in the matrix and its conservation inside the matrix during cryonics.

As regards the implementation of the process as a whole, it is possible to chain the stages of the process one after the other and in particular to carry out the lyophilization stage immediately after the cryogenics stage. In addition, the process can be carried out continuously. It is also possible to keep the product in frozen form at the end of the cryogenics step and to carry out the lyophilization subsequently, after a negative cold storage time to keep the products in the solid state (for example at - 20 ° C). In both cases, the advantage of the process is retained.

Thus, according to alternative embodiments, the lyophilization step can be carried out either immediately following the cryogenics step, or subsequently after storage of said frozen granules, particles or beads.

The conditions of the process can be adapted according to the shape of the matrix to be dehydrated, in particular the pressure during the cryogenic step, and the lyophilization parameters. Those skilled in the art will know how to make such adaptations.

Advantageously, the matrix obtained by treating the plant material is transferred rapidly to the gas dissolution and cryogenics apparatus in order to limit the degradation or denaturation of the compounds.

The term “plant material” within the meaning of the invention is understood to mean plants in the general sense, considering that all plant material is odorous, the intensity of this odor being able to vary. It may be in particular flowers or parts of flowers such as the petals, pistils, leaves, stems, but also herbaceous plants such as aromatic herbs, fruits of any type such as raspberries, lychees, apples, vanilla pods or roots such as ginger, or spices. The plant material is preferably fresh, or freshly cut, so that the odorous molecules are not altered, and that the odor emanating from the plant material is as close as possible to the natural state. In a preferred embodiment, the plant material consists of flowers and its different parts, in particular the petals.

By "treatment" of the plant material is meant any transformation of the plant material into a liquid, semi-liquid or pasty matrix such as mechanical extraction (using a juice extractor), pressing, mixing. .

By “silent flower” within the meaning of the invention, is meant a flower from which neither essence nor absolute can be extracted. The techniques known to date to those skilled in the art of perfumery, such as extraction by volatile solvents and steam distillation, do not make it possible to extract their perfume. Among the mute flowers are, for example, lily, violet, hyacinth, duddleia, peony, freesia, lily of the valley, honeysuckle, gardenia, carnation, pittosporum, syringa, sweet pea , glycine and heliotrope. Thus, in a preferred embodiment of the invention, the plant material originates from a mute flower.

In another preferred embodiment of the invention, the plant material consists exclusively of petals or exclusively of petals and pistils of flowers.

A second subject of the invention relates to a natural odorous ingredient obtained according to the process described above, in the form of frozen granules, particles or balls.

A third subject of the invention relates to a natural odorous ingredient obtained according to the process described above, which is in the form of a dehydrated powder.

This powder can be 100% derived from the fragrant plant material. Such a product, if it is technically feasible (sufficient yield, non-oily extracted product, etc.) will be very concentrated, which can be a high quality index.

The powder may also contain, in addition to the plant material, a support which makes it possible to fix the odorous molecules. Such a support can consist of maltodextrins or of a natural vegetable support for a 100% vegetable ingredient.

In a preferred embodiment of the invention, the fragrant ingredient which is provided in frozen form or as a dehydrated powder is obtained from a mute flower.

A fourth subject of the invention relates to an odorous composition comprising at least one odorous ingredient as defined above.

In a preferred embodiment of the invention, such a composition comprises at least one fragrant ingredient obtained from a mute flower. A fifth subject of the invention relates to a process for preparing a liquid odorous composition comprising a step of dissolving at least one odorous ingredient in the form of a dehydrated powder as defined above.

The fragrant ingredients and the compositions containing them can be used in perfumery, namely in body perfumes and room fragrances, but also in cosmetics.

The present invention is illustrated with the aid of the following examples, which should in no way be considered as limiting the scope of the present invention.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1: Chromatograms obtained following analysis by a Héraclès II electronic nose of AlphaMos (double ultra-rapid gas phase chromatography) of the lilac powders prepared by applying the extraction process according to the invention (A: column 1; B: column 2) .

EXAMPLES

EXAMPLE 1 Preparation of lilac powders

Preparation process

White lilac and purple lilac flowers were harvested and processed separately.

The petals were separated from the flowers manually before being passed through an ANGEL 7500 horizontal juice extractor. The juice thus collected was immediately treated in equipment allowing it to be cryogenized while trapping dissolved gas therein, according to the process described in patent WO2019 / 234341 for example. The frozen beads thus obtained were then lyophilized according to standard conditions in a CHRIST alpha 1-8 freeze-dryer, until “dry” powders were obtained (more weight loss measured).

Characteristics of powders

The first remarkable element comes from the quantity of powder thus obtained. For the two flowers treated, the powder yields were around 5%, which is very high since no support was added and it is therefore only material initially present in the flowers. petals. Lyophilization supports are generally added to the preparations to be lyophilized, in order to guarantee the presence of a sufficient dry extract for the binding of molecules of interest during the treatment and also to reduce production costs. The yield obtained during this preparation is already very convincing on these two points without having to add anything. The second very remarkable element is the smell of the products thus obtained, which were very clearly identified as being those of the two respective flowers by the various panels consulted. Electronic nose analyzes (Figures IA and IB) have also made it possible to confirm the presence in the product of characteristic peaks associated with chemical compounds known to be significant contributors to the scents of lilac flowers:

(E) -ocimere, which is the major component; lilac aldehydes and lilac alcohols, which each have several dimers and are among the most characteristic compounds; benzyl methyl ether, 1,4-dimethoxybenzene and indole, which are the other characteristic compounds of the scent of lilac.

Peaks were identified on the chromatograms using their retention indices on each column. The reference data used are those of the software coupled to the Héraclès II measuring device and of the NIST WebBook available in particular from the address: https://webbook.nist.gOv/chemistry/#Search.

As lilac is one of the so-called "dumb" flowers, it is all the more remarkable to have succeeded in obtaining, in relatively large quantities, a product that conforms in terms of odor that can be used as ingredients for perfumery or cosmetic products. cosmetic.

EXAMPLE 2 Preparation of jasmine powders

Jasmine flowers were collected. The petals and pistils were separated manually before being passed through an ANGEL 7500 horizontal juice extractor. A portion of the juices thus collected were immediately treated in equipment allowing them to be cryogenized while trapping dissolved gas therein, according to the report. process described in patent WO2019 / 234341 for example. The frozen beads thus obtained were then lyophilized according to standard conditions in a CHRIST alpha 1-8 freeze-dryer, until “dry” powders were obtained (no more weight loss measured). In the other juice fractions, representing 200 g each, 50 g of maltodextrins were added each time, then the mixtures thus obtained underwent the same process as described above, until powders were obtained.

The powder yields thus obtained are:

About 5% for the petals without addition of maltodextrins;

About 10% for the pistils without addition of maltodextrins;

About 30% for the petals with the addition of maltodextrins;

About 35% for the pistils with the addition of maltodextrins;

All the products obtained have an odor very similar to that of the initial flower.

The choice of whether or not to add a support such as maltodextrins depends on the starting matrix and on the desired product quality. For certain products, the dry powder alone can become liquid again, this is the case in particular when the oily fraction is too large; it is then necessary to add a support at the time of lyophilization. On the other hand, by adding a support, we increase the yield as illustrated above, which is economically advantageous, and allows the standardization of products.

5

Claims

1. Process for preparing an odorous ingredient in solid form from a plant material comprising the steps of: a) Disposing of a plant material b) Carrying out a treatment of said plant material, optionally under an inert atmosphere, in order to have a product in the form of a liquid, semi-liquid or pasty matrix c) Dissolve a gas in said matrix by passing through a zone dense in gas molecules, such a density being obtained (i) either by means of a flow gas generated by the evaporation of a cryogenic fluid, (ii) or by an increase in pressure; d) Cryogenizing said gas-rich matrix obtained in step c) under pressure and temperature conditions making it possible to maintain said trapped gas in order to obtain frozen granules, particles or beads;

2. The method of claim 1 further comprising the steps of: a) freeze-drying said granules, particles or beads; b) Obtaining said fragrant extract in the form of a dehydrated powder.

3. Method according to one of the preceding claims wherein said plant material is from a mute flower.

4. The method of claim 3 wherein said mute flower is selected from lily, violet, hyacinth, buddleia, lilac, peony, freesia, lily of the valley, honeysuckle, gardenia, carnation, pittosporum, syringa, sweet pea, wisteria and heliotrope.

5. Method according to one of the preceding claims wherein said plant material consists exclusively of petals.

6. Natural odorous ingredient obtained according to the process defined in one of claims 1, 3, 4 or 5 in the form of frozen granules, particles or beads.

7. Natural odorous ingredient obtained according to the process defined in one of claims 1 to 5 in the form of a dehydrated powder.

8. Ingredient according to one of claims 6 or 7 obtained from a mute flower.

9. A fragrant composition comprising at least one fragrant ingredient obtained from a mute flower as defined in claim 8.

10. Process for preparing a liquid odorous composition comprising a step of dissolving at least one odorous ingredient as defined in one of claims 7 or 8.