HK1195714A - Solid/liquid extraction using a solvent comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms - Google Patents

Description

Solid/liquid extraction with a solvent comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms

Technical Field

The present invention relates to a process for the solid/liquid extraction of a natural extract (in particular oil or butter), in particular comprising a high unsaponifiable matter content, from vegetable solid materials or microorganisms.

Background

The unsaponifiable matter or fraction of unsaponifiable matter (fraction) consists of compounds which remain insoluble in water and can be extracted by organic solvents after the continued action of a basic matrix (base alcaline).

Most unsaponifiables of vegetable oils comprise a major family of substances. Among these main families, mention may be made of saturated or unsaturated hydrocarbons, aliphatic or terpenoid alcohols, sterols, tocopherols, carotenoid pigments, xanthophylls, and one or two specific families for certain oils.

Conventional processes for obtaining unsaponifiables from vegetable oils aim at extracting the main family that makes up all or part of them, allowing the preparation of partial or total fractions of unsaponifiables.

Some or all of the unsaponifiable fractions are particularly sought after for their pharmacological, cosmetic and nutritional properties.

The conventional method for obtaining unsaponifiables comprises, inter alia, a step of saponifying the fat and a step of extracting the desired product (unsaponifiable) with an organic solvent.

The most commonly used solvents for the extraction of oil or butter (especially unsaponifiable-matter rich oil or butter) from vegetable solid materials or microorganisms are aliphatic solvents (and especially hexane) and fatty acid esters containing more than 10 carbon atoms (and especially methyl palmitate, methyl stearate and ethyl decanoate).

Hexane in particular involves the disadvantage of having toxicity, in particular it is classified as a grade 3 CMR in the UE1CMR list or in the UE2CMR list.

Hexane further involves the disadvantage of being dangerous to handle, especially due to its physicochemical properties, in particular its flash point (-23.3 ℃) and/or its autoignition temperature (233.9 ℃).

Fatty acid esters involve the disadvantage of having a high boiling point (typically above 185 ℃); due to the high temperatures required, its removal by distillation is very energy-consuming and may impair the quality of the extracted unsaponifiable fraction.

Finally, processes involving conventional aliphatic solvents (and hexane in particular) may be unsatisfactory in terms of: yield relative to the oil or butter and/or relative to the unsaponifiable matter content of the oil or butter obtained, in particular the extraction rate, selectivity, simplicity, cost, toxicity, ecotoxicity, convenience, number of steps, in particular the extraction and/or speed, of the particular unsaponifiable matter fraction or fractions.

Furthermore, the process for obtaining the oil may require, both economically and environmentally, the use of a certain amount of organic solvent that is not compatible with the feasibility of the process, have an unsatisfactory number of extraction steps and/or be too slow.

Disclosure of Invention

It is therefore an object of the present invention to address all or part of the problems mentioned above. In particular, the object of the present invention is to provide a process with higher overall yield, suitable for obtaining oils or butters with higher unsaponifiable matter content or showing a specific spectrum, which is more economical, more direct, more environmentally friendly, requires lower amounts of organic solvents, is easier to use, is faster, produces less toxic conditions, is suitable for obtaining oils or butters, in particular with high unsaponifiable matter content and at least corresponds to (or even better than) the yield and/or selectivity of the existing processes.

In particular, there is a need to find solvents which are less toxic, in particular not classified as CMR substances (in particular UE2CMR substances), and/or suitable for the extraction of oils or butters, and whose yield and/or selectivity are at least comparable to those obtained using conventional aliphatic solvents (in particular hexane) and fatty acid esters (in particular methyl stearate).

Solvents "classified as CMR substances" may be those mentioned in the list of the appendix of the 2009/2/CE directive on 15 th 1/2009, which is referred to hereinafter as the "UE 1CMR list", those listed in the European regulatory Classification for carcinogenic, mutagenic and toxic Chemicals-31 st ATP,2009 (la Classification emission ene ne glement products rog nes, mug nes et toxiques point of spread reduction-31 eATP, 2009), which second list is referred to hereinafter as the "UE 2CMR list", and/or known to be responsible for the development of cancer by the public health department of California, the department of occupational health, the California safety cosmetology (California patent of health, the calcium nutrient company 2005 or the combination of cosmetic substances known to result in the development of cancer (the calcium chemical) on 1 th 1/2009, California chemical company code 2005 or the chemical company chemical safety code 2005 or the combined toxicity of the cosmetic product (calcium patent publication) of the cosmetic product Those listed in the list of house organic purity), which is referred to hereinafter as the US CMR List.

When the expression UE CMR list is used herein, this means a UE1CMR list and/or a UE2CMR list, and in particular a UE2CMR list.

The solvents used in the context of the present invention are therefore free of the following solvent families and solvents:

certain alkanes, such as hexane, heptane, etc.,

certain aromatic hydrocarbons, such as naphthalene,

certain halogenated solvents, in particular chlorinated solvents (1, 2-dichloroethane or DCE, trichloroethane, dichloromethane, trichloromethane (chloroform), dichloroethylene, carbon tetrachloride, etc.), or 1-chlorobutane.

In particular, the aim of the process according to the invention may be to increase the yield of natural extracts (in particular oils or butters) and/or the content of unsaponifiables contained in such extracts.

The present invention therefore relates to a process for the solid/liquid extraction of a natural extract contained in at least one plant solid material or microorganism, in particular said natural extract comprising or consisting of oil or butter, in particular with a high unsaponifiable matter content, said process comprising at least the following steps:

-solid/liquid extraction of at least one plant solid material or microorganism by means of a first solvent system comprising a solvent in a content of at least 50% by volume, relative to the total volume of the first solvent system, chosen from solvents comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions,

-recovering a natural extract, in particular a natural extract comprising or consisting of oil or butter, in particular a natural extract rich in unsaponifiables.

According to the invention, the term "natural extract" refers to a plant, mineral or animal extract.

According to the present invention, the term "solvent system" refers to a single solvent or a mixture of solvents.

The term "microorganism" refers to any living microscopic organism, such as bacteria and/or fungi, in particular yeasts and molds.

Typically, the solid/liquid extraction is performed by contacting at least one plant solid material and/or microorganism with a hot first solvent system.

According to a particular embodiment, the solid/liquid extraction is carried out using a soxhlet extractor. In this particular case, it is advantageous to heat the solvent to reflux for extraction.

In the recovery step, the natural extract may be recovered, in particular by solvent extraction, filtration and/or crystallization.

If the first solvent system comprises a solvent or solvent mixture in an amount selected from the list of X%, this means that the percentage of complementarity corresponds to one or more organic solvents not present in the list.

According to a particular embodiment, the first solvent system is free of tert-butyl ether (in particular ETBE and/or MTBE) or terpenes (in particular limonene and alpha-pinene).

In particular, the solvent comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms is selected from the group consisting of methyl ketones (in particular methyl isobutyl ketone or MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular diisopropyl ether or DIPE), cyclic ethers, and mixtures thereof.

CAS numbers for these different solvents are as follows: methyl isobutyl ketone or MIBK: 108-10-1; 2-heptanone: 110-43-0; ethyl propionate: 105-37-3; butyl propionate: 590-01-2; isoamyl propionate: 105-68-0; diisopropyl ether or DIPE: 108-20-3.

According to the invention, the term "high unsaponifiable matter content" means that the oil or butter comprises at least 1% by weight, especially at least 2% by weight, and especially at least 3% by weight of unsaponifiable compounds originally present in the solid material.

In particular, the process according to the invention may be free of a complexation step involving the first solvent system.

The first solvent system may comprise a solvent chosen from solvents comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of an ether function, or a ketone function, or an ester function, in particular chosen from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), and mixtures thereof, in a content of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, even more in particular at least 99% by volume, relative to the total volume of the first solvent system.

In particular, the first solvent system consists of a solvent comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in particular selected from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), or mixtures thereof.

The first solvent system may comprise a solvent in a content of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, even more in particular at least 99% by volume, relative to the total volume of the first solvent system, selected from solvents comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functional groups, or ketone functional groups, or ester functional groups, in particular from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), or mixtures thereof.

According to an alternative embodiment, the first solvent system consists of a solvent chosen from solvents comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in particular chosen from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), and propyl ethers (in particular DIPE).

According to a particular embodiment, the first solvent system has a density of less than 1 (and in particular less than or equal to 0.9).

Advantageously, according to the invention, the first solvent system further comprises Hexamethyldisiloxane (HMDS) in a content typically comprised between 0.1 and 49% by volume with respect to the total volume of said first solvent system.

The CAS number of HMDS is 107-46-0.

According to a particular embodiment, the first solvent system may comprise:

-a content of at least 50% by volume, relative to the total volume of the first solvent system, of a solvent chosen from solvents comprising at least 5 carbon atoms (in particular from 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, and

-HMDS in a content range in particular from 0.1 to 49% by volume, more particularly from 0.5 to 30% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the first solvent system.

The first solvent system may comprise:

-a content of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, of a solvent, relative to the total volume of the first solvent system, chosen from solvents comprising at least 5 carbon atoms (or even 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in particular chosen from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), and mixtures thereof, and

-HMDS in a content range in particular from 0.1 to 40% by volume, more particularly from 0.5 to 25% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the first solvent system.

In particular, the first solvent system consists of the following components:

-a solvent comprising at least 5 carbon atoms (or even 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in particular selected from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), and mixtures thereof, in a content advantageously of at least 50% by volume, relative to the total volume of the first solvent system, and

-HMDS in a content range in particular from 0.1 to 49% by volume, more particularly from 0.5 to 30% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the first solvent system.

The first solvent system may comprise:

-a content of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, even more in particular at least 99% by volume, relative to the total volume of the first solvent system, of a solvent selected from solvents comprising at least 5 carbon atoms (or even 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of ether ester functions, or ketone ester functions, or ester functions, in particular from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), and

-HMDS in a content range in particular from 0.1 to 40% by volume, more particularly from 0.5 to 25% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the first solvent system.

According to an alternative embodiment, the first solvent system consists of:

-a solvent comprising at least 5 carbon atoms (or even 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in a content advantageously of at least 50% by volume relative to the total volume of the first solvent system, in particular selected from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), and propyl ethers (in particular DIPE), and

-HMDS in a content range in particular from 0.1 to 49% by volume, more particularly from 0.5 to 25% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the first solvent system.

According to a particular embodiment, the first solvent system comprises a CMR solvent in a content of less than or equal to 10% by volume, in particular less than or equal to 5% by volume, in particular less than or equal to 2% by volume, more in particular less than or equal to 1% by volume, even more in particular less than or equal to 0.5% by volume, or even less than or equal to 0.1% by volume, relative to the total volume of said first solvent system, in particular the CMR solvents proposed in the list of UE1, UE2 and/or US CMR.

Even more particularly, the first solvent system is free of solvents set forth in the list of UE1, UE2, and/or US CMR, and more particularly hexane and dichloroethane.

The solvent used in the first solvent system has a purity of at least 90%, particularly at least 95%, particularly at least 98%, more particularly at least 99%, or even at least 99.5%.

The invention also relates to a process for obtaining an unsaponifiable fraction, in particular a whole or partial fraction, comprising at least the following steps:

-solid/liquid extraction of at least one plant solid material or microorganism by means of a first solvent system comprising a solvent in a content of at least 50% by volume, relative to the total volume of the first solvent system, selected from solvents comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions, in particular from methyl ketones (in particular MIBK, 2-heptanone), propionic acid esters (in particular ethyl propionate, n-butyl propionate, isoamyl propionate), propyl ethers (in particular DIPE), and mixtures thereof,

advantageously recovering a natural extract rich in oil or butter, in particular in the form of an organic solvent rich in oil or butter, or even recovering an oil or butter, in particular said natural extract rich in unsaponifiables,

-converting the oil or butter into a water-alcohol solution by a saponification step,

-extracting the aqueous-alcoholic solution, wherein the fat fraction is separated from the unsaponifiable fraction by liquid/liquid extraction, and

-recovering an unsaponifiable fraction, in particular a partial or total fraction.

According to the invention, the term "total fraction" means that said fraction comprises all families of substances forming unsaponifiables contained in the vegetable oil or butter or microorganisms considered.

According to the invention, the term "partial fraction" means that said fraction comprises at least one family of substances forming unsaponifiables contained in the vegetable oil or butter or microorganism under consideration.

The first solvent system is defined in terms of the method used for solid/liquid extraction of plant extracts.

Particularly advantageously, the solid/liquid extraction solvent according to the invention comprises from 5 to 8 carbon atoms and therefore has a short carbon chain, so that it is advantageous to be sufficiently lipophilic to extract the oil and/or butter and unsaponifiable fractions contained therein, and suitable to be easily separated subsequently from the extract obtained.

The conversion of the natural extract, in particular the oil or the butter, into a water-alcohol solution can be carried out in a conventional solvent system.

According to a particular alternative embodiment, the conversion of said natural extract (in particular said oil or said butter) into a water-alcohol solution can be carried out in a second solvent system comprising or even consisting of at least one solvent from the first solvent system.

More particularly, the transformation may be carried out without complete purification of the natural extract (in particular oil or butter). In particular, the conversion is carried out directly on the basis of an organic solution enriched in said natural extract (in particular an organic solution enriched in oil or butter), in particular comprising at least 2% by weight, in particular at least 5% by weight, or even at least 10% by weight of oil or butter relative to the total weight of the organic solution enriched in oil or butter.

According to a first alternative embodiment, the conversion is carried out on a distillate fraction, in particular a partially evaporated distillate fraction, to which less than 50% by weight of other solvents are added, or even no other solvents are added.

According to another alternative embodiment, at least 10% of at least one other solvent (such as C2 to C4 alcohols, especially ethanol, n-propanol, isopropanol, butanol, especially n-butanol, methyl tetrahydrofuran (MeTHF) and mixtures thereof) may be added to the oil or butter rich organic solution, especially the evaporated oil or butter rich organic solution.

When the aqueous-alcoholic solution is extracted by liquid/liquid extraction, it can be carried out using a third solvent system, in the same way as defined for the first solvent system. In particular, the third solvent system comprises or consists of the same solvent as the user in the first and/or second solvent system.

As a general rule, the solid/liquid extraction process according to the invention may be more economical, more direct, more environmentally friendly, require lower amounts of organic solvents, be easier to use, be faster, produce less toxic conditions, be suitable for obtaining oils or butters, in particular with high unsaponifiable content and with a yield and/or selectivity at least comparable to (or even superior to) existing processes.

The saponified and unsaponifiable matter extraction fraction can be carried out in particular according to the method described in EP 1246633.

The plant solid material or microorganism used in the process of the invention may be obtained from soybean, rape, corn, sunflower, sesame, lupine, cotton, coconut, olive, avocado, cocoa, illipe, shea, palm kernel, peanut, coconut kernel, linseed, castor bean, grape seed, cucurbit seed, blackcurrant seed, melon seed, tomato seed, pumpkin seed, almond, hazelnut, walnut, evening primrose, borage, safflower, camelina, poppy, giant algae, microalgae (such as haematococcus pluvialis (haemantocococcus), Dunaliella (Dunaliella), Spirulina (Spirulina), chlorella (chlorella)), and/or microorganisms, in particular marine, freshwater or terrestrial microorganisms, in particular yeasts, molds, and more in particular bacteria, and mixtures thereof.

Typically, the obtained unsaponifiable fraction ranges from 2 to 10% in avocado oil, about 0.5% in coconut oil, about 1% in soybean oil and about 1% in olive oil.

The person skilled in the art knows the methods for extracting the unsaponifiable fraction of vegetable oils or butter or microorganisms and knows how to apply it to the conversion, extraction and/or recovery of the unsaponifiable according to the invention.

Among the prior art relating to this sector, mention may be made in particular of the processes for preparing the avocado oil unsaponifiable matter, as described and claimed in patent FR 2678632.

In this way, before the extraction and saponification of the oil, the avocado oil unsaponifiable matter can be prepared from the fruit which has been previously heat-treated, as described in patent FR 2678632.

The heat treatment consists of the controlled drying of the fruit, preferably fresh fruit, at a temperature of at least about 80 ℃ (and preferably between about 80 ℃ and about 120 ℃), preferably for at least 4 hours (advantageously for at least 10 hours, preferably between about 24 hours and about 48 hours).

Mention may also be made of a process for preparing soybean oil unsaponifiables, obtained from a concentrate of soybean oil unsaponifiables.

The concentrate of unsaponifiables can be prepared by molecular distillation according to the method described in patent application FR2762512 for lupin oil (but applicable to soybean oil).

In this process, soybean oil is distilled in a centrifugal or wiped film molecular still at a temperature of between about 210 to 250 ℃ and under high vacuum of 0.01 to 0.001 mm hg (or 0.13 to 1.3 Pa).

The distillate obtained has an unsaponifiable content of between 5 and 40% by volume and therefore constitutes a concentrate of the soybean unsaponifiable matter.

The concentrate is then saponified with a base such as oxaline or soda in a polar medium (especially an alcoholic medium, preferably ethanol, n-propanol, isopropanol, butanol (especially n-butanol), methyltetrahydrofuran (MeTHF), or a mixture thereof) and subjected to one or more extractions by a third solvent system.

Subsequently, the obtained extract is preferably centrifuged, filtered, and then washed with water to eliminate residual traces of alkali.

The extraction solvent was evaporated thoroughly to recover the unsaponifiable matter. It is also obviously possible to envisage additional operations known to the person skilled in the art, such as a deodorization step.

Finally, the natural extract (in particular oil or butter) can be pre-enriched in unsaponifiables by separating most of the components of the unsaponifiables recovered in the concentrate before their saponification. Various methods may be used: freezing crystallization, liquid/liquid extraction or molecular distillation.

The initial concentration of unsaponifiable oil or butter can reduce the volume of the natural extract (in particular oil or butter) to be saponified.

Molecular distillation is particularly preferred, preferably at a temperature of between about 180 to about 230 ℃, by maintaining the pressureIs held at 10^-3To 10^-2Between mm Hg and preferably 10^-3In mm Hg.

The concentration of unsaponifiables of the distillate can reach 60% by weight relative to the total weight.

More particularly, the invention relates to a process as described in the present specification, in which the unsaponifiable matter obtained is chosen from soybean unsaponifiables (advantageously enriched in sterols, tocopherols and/or squalene), avocado unsaponifiables, in particular avocado unsaponifiables enriched in furan-type fractions and/or avocado unsaponifiables enriched in sterol-type fractions and/or avocado unsaponifiables enriched in trihydroxylated compounds.

The invention further relates to an oil or butter free of solvents classified in the UE1CMR list, the UE2CMR list and/or the US CMR list, in particular suitable for obtaining (or directly obtaining) said oil or said butter by a method according to the invention.

The invention further relates to an unsaponifiable fraction, in particular a partial or total fraction, which is free of solvents classified in the list of UE1, UE2 and/or US CMR, in particular which can be obtained by the process according to the invention.

The invention further relates to the use of the fraction, the natural extract, the butter or the oil for the preparation of a composition (in particular a pharmaceutical, nutritional and/or cosmetic composition) or a nutritional supplement.

The invention also relates to an unsaponifiable fraction (in particular a fraction that is partially or totally), an oil or a butter that is free of solvents classified in the list of UE1, UE2 and/or US CMR, as described above, for use as a medicament, medical device, dermatological agent, cosmetic agent, or nutraceutical for human or animal use, advantageously for preventing and/or treating connective tissue diseases such as arthrosis, joint diseases such as osteoarthrosis, periodontal diseases such as gingivitis or periodontitis, or even for preventing and/or treating dermal or subcutaneous tissue diseases such as skin ageing, stretch marks and orange peel, or epidermal barrier diseases such as skin inflammation, atopic eczema and irritant and/or inflammatory dermatitis.

The invention further relates to a composition (especially a nutritional, cosmetic or pharmaceutical composition) or nutritional supplement comprising a natural extract, oil, butter or unsaponifiable fraction derived from at least one natural extract, vegetable oil or butter or microorganism, said extract, oil, butter or fraction being free of solvents classified in the list of UE1, UE2 and/or US CMR and/or being suitable for obtaining or directly obtaining said extract, oil, butter or fraction by the method according to the invention, and optionally comprising excipients, especially cosmetically, nutritionally or pharmaceutically acceptable excipients.

According to a particular embodiment, the invention relates to a composition (in particular a nutritional, cosmetic or pharmaceutical composition) or a nutritional supplement comprising at least one unsaponifiable substance (in particular a soybean unsaponifiable substance, an avocado unsaponifiable substance, more particularly an avocado unsaponifiable substance rich in a furanic fraction and/or an avocado unsaponifiable substance rich in a sterol fraction), said unsaponifiable substance being suitable for being obtained or directly obtained by the method according to the invention.

The pharmaceutical composition, nutritional composition or nutritional supplement may be intended for the prevention and/or treatment of connective tissue diseases (especially arthrosis), periodontal diseases, skin aging and/or skin inflammation.

The pharmaceutical or cosmetic composition according to the invention may be intended for the prevention and/or treatment of skin diseases of the epidermal, dermal and/or subcutaneous tissue.

According to the invention, the term "free of solvents classified in the list of UE1, UE2 and/or US CMR" means that the total content of solvents classified in the list of UE1, UE2 and/or US CMR is less than 10ppm, in particular less than 5ppm, in particular less than 2ppm, or even less than 1 ppm.

The invention further relates to a cosmetic treatment process wherein the cosmetic composition according to the invention is applied topically.

The invention also relates to a plant extract, oil, butter or unsaponifiable matter derived from a vegetable oil or butter or a microorganism obtained or suitable for obtaining by the method according to the invention for use as a medicament, in particular for the treatment or prevention of connective tissue diseases (and especially arthrosis).

According to another aspect, the invention relates to the use of HMDS in a content ranging from 0.1 to 49% by volume (typically from 0.1 to 45% by volume) relative to the total volume of the extraction solvent or extraction system in a solid/liquid extraction process, in particular of unsaponifiables, advantageously a solid/liquid extraction process from plant solid materials or microorganisms.

HMDS may be present in an amount ranging from 0.5 to 25% by volume, or even from 1 to 20% by volume, and more particularly from 5 to 10% by volume, relative to the total volume of the solvent.

In particular, the method comprises a solvent system comprising:

at least one solvent comprising at least 5 carbon atoms (or even 5 to 8 carbon atoms) and 1 or 2 oxygen atoms in the form of an ether, ketone or ester function, in particular at least one solvent chosen from

Methyl ketones, in particular MIBK, 2-heptanone,

esters of propionic acid, in particular ethyl propionate, n-butyl propionate, isoamyl propionate,

the propylene ethers, in particular DIPE,

a mixture thereof, or

-at least one solvent selected from

Fluorinated aromatic solvents, in particular trifluorotoluene (BTF) and hexafluorobenzene (BHF),

o tert-butyl ether, in particular 2-ethoxy-2-methylpropane, also known as ethyl tert-butyl ether (ETBE), and 2-methoxy-2-methylpropane, also known as methyl tert-butyl ether (MTBE),

solvents containing at least one silicon atom, in particular Hexamethyldisiloxane (HMDS) and Tetramethylsilane (TMS),

methyl tetrahydrofuran (MeTHF), and

a mixture thereof, or

-mixtures of the above solvents.

The content of these solvents may be as described above.

CAS numbers for these different solvents are as follows: BTF: 98-08-8; BHF: 392-56-3; ETBE: 637-92-3; MTBE: 1634-04-4; TMS: 75-76-3; and MeTHF: 96-47-9.

The presence of HMDS in the extraction solvent may be suitable for refining the spectrum of unsaponifiables obtained, increasing the extraction yield of one or more of the fractions and/or the overall yield of the extraction.

HMDS may be particularly suitable for adjusting the extraction capacity of the solvent system. In this way, the HMDS present in the extraction solvent may be suitable for increasing the yield of the oil and/or for increasing the unsaponifiable content of the oil, the spectrum of the unsaponifiable obtained from the refining and/or the extraction rate of one or more fractions.

Furthermore, the HMDS present in the solvent system in the amounts as defined above may be suitable to reduce the consumption of solvent and/or the extraction time.

In this way, HMDS can be used as an agent to increase the extraction yield, an agent to increase the unsaponifiable content of the natural extract and/or an accelerator.

Of course, different features disclosed in this specification may be combined together.

By way of illustration of embodiments of the invention, the following experiments have been conducted.

Detailed Description

Examples

In all examples, reference experiments were performed using hexane.

Example 1: extraction using dried avocados

Hexane (reference) was used and the following solvents were used: 2-heptanone, MIBK and ethyl propionate were extracted from dried avocado.

The dried avocados were ground and introduced into cellulose pillars (cartouche) (30 to 40 g). The extraction was carried out in a Soxhlet apparatus (BUCHI B-811). Then, four sets of extractions were run in parallel, each for 20 extraction/siphon cycles. Once the extraction has been completed, the extraction solvent is evaporated and the desolventized residue is weighed. Then, the weight yields were compared. The results are shown in Table 1.

TABLE 1

The weight extraction yield is equal to:

r =100 × (weight of extract/weight of solid material used)

The unsaponifiable matter content of the natural extract was calculated by gas chromatography.

The increase in unsaponifiable matter content of the natural extract is calculated as follows:

a =100 × (unsaponifiable matter content of natural extract obtained with solvent S-unsaponifiable matter content of natural extract obtained with hexane)/unsaponifiable matter content of natural extract obtained with hexane.

These results show that the solvent according to the invention has an extraction yield equal to or even superior to that of hexane. In any case, the unsaponifiable matter content of the obtained natural extract is greater than that of the reference natural extract obtained with hexane, increasing by a range of 1.9 to 9.5%.

Example 2: extraction of ground lupin shells

Following the procedure in example 1 and using the following solvents: 2-heptanone, MIBK, ethyl propionate and isopropyl ether were subjected to extraction of ground lupin shells. The results are shown in Table 2.

TABLE 2

The weight extraction yield is equal to:

r =100 × (weight of extract/weight of solid material used)

The increase in weight extraction yield was calculated as follows:

a' =100 × (weight extraction yield obtained with solvent S-weight extraction yield obtained with hexane)/weight extraction yield obtained with hexane

The unsaponifiable matter content of the natural extract was calculated by gas chromatography.

The extraction rate of unsaponifiables per 100g of solid material is calculated as follows:

t = (weight extraction yield x unsaponifiable matter content)/100.

These results show that the solvent according to the invention is suitable for increasing the gravimetric extraction yield compared to the gravimetric extraction yield of hexane. The increase in weight extraction yield ranged from 6.5% with DIPE to 53.8% with 2-heptanone.

The extraction of unsaponifiables per 100g of solid material used, with the exception of DIPE, was equal to or greater than that obtained with hexane.

Example 3: extraction using lupin seed meal

Extraction of lupin seed meal was performed with hexane (reference) and with MIBK.

60g of lupin seed meal was introduced into a cellulose column. The extraction was carried out in a Soxhlet apparatus (BUCHI B-811). Then, four sets of extractions were run in parallel, two for each solvent; each corresponding to 20 extraction/siphon cycles. Once the extraction has been completed, the extraction solvent is evaporated and the desolventized residue is weighed. Then, the weight yields were compared. The oil was then analyzed for its unsaponifiable composition. The average results are shown in table 3.

TABLE 3

MIBK (non-CMR solvent) was adapted to increase the extraction yield of oil by 0.5%. In addition to lower toxicity, MIBK offers the advantage of increasing the extraction yield for a particular unsaponifiable fraction (carotenoid) by nearly 52% by weight, highlighting the low degradation of the family of compounds during the extraction step.

Claims (16)

1. Process for the solid/liquid extraction of a natural extract contained in at least one plant solid material or microorganism, comprising at least the following steps:

-solid/liquid extraction of at least one plant solid material or microorganism by means of a first solvent system comprising a solvent in a content of at least 50% by volume, relative to the total volume of the first solvent system, chosen from solvents comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions,

-recovering a natural extract, in particular a natural extract comprising oil or butter, in particular a natural extract rich in unsaponifiables.

2. Process for obtaining an unsaponifiable fraction, in particular a whole or partial fraction, comprising at least the following steps:

-solid/liquid extraction of at least one plant solid material or microorganism by means of a first solvent system comprising a solvent in a content of at least 50% by volume, relative to the total volume of the first solvent system, chosen from solvents comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of ether functions, or ketone functions, or ester functions,

-optionally recovering the organic solvent enriched in natural extracts,

-converting said natural extract into a water-alcohol solution by a saponification step,

-extracting the aqueous-alcoholic solution, wherein the fat fraction is separated from the unsaponifiable fraction by liquid/liquid extraction, and

-recovering the unsaponifiable fraction.

3. The method of claim 1 or 2, wherein the first solvent system has a density of less than 1.

4. Process according to any one of claims 1 to 3, characterized in that the solvent comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms is selected from methyl ketones, in particular MIBK, 2-heptanone, propionic acid esters, in particular ethyl propionate, n-butyl propionate, isoamyl propionate, propyl ethers, in particular DIPE, and mixtures thereof.

5. Process according to any one of claims 1 to 4, characterized in that the first solvent system comprises a content of solvent of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, even more in particular at least 99% by volume, relative to the total volume of the first solvent system, the solvent comprising from 5 to 8 carbon atoms and 1 or 2 oxygen atoms.

6. Process according to any one of claims 1 to 5, characterized in that the first solvent system may comprise a content of at least 60% by volume, in particular at least 75% by volume, in particular at least 90% by volume, more in particular at least 95% by volume, even more in particular at least 99% by volume, relative to the total volume of the first solvent system, of a solvent selected from solvents comprising 5 to 8 carbon atoms and 1 or 2 oxygen atoms in the form of an ether function, or a ketone function, or an ester function, in particular from methylketones, in particular from MIBK, 2-heptanone, propionic acid esters, in particular ethyl propionate, n-butyl propionate, isoamyl propionate, and propyl ethers, in particular DIPE.

7. Process according to any one of claims 1 to 6, characterized in that the first solvent system further comprises HMDS, advantageously in a content of between 0.1 and 49% by volume relative to the total volume of the first solvent system.

8. The method according to any one of claims 1 to 7, characterized in that the first solvent system comprises a CMR solvent in a content of less than or equal to 10% by volume, in particular less than or equal to 5% by volume, in particular less than or equal to 2% by volume, more in particular less than or equal to 1% by volume, even more in particular less than or equal to 0.5% by volume, or even less than or equal to 0.1% by volume, relative to the total volume of the first solvent system, in particular CMR solvents as set forth in the list of UE1, UE2, and/or US CMR.

9. Process according to any one of claims 2 to 8, characterized in that the conversion of said natural extract into a water-alcohol solution is carried out in a second solvent system comprising at least one solvent selected from the group consisting of C2 to C4 alcohols, and in particular ethanol, n-propanol, isopropanol, butanol, in particular n-butanol, MeTHF and mixtures thereof, in a content of at least 10% by volume relative to the total volume of said second solvent system, said second solvent system being suitable for being added to an oil-rich organic solution, in particular an evaporated oil-rich organic solution.

10. Process according to any one of claims 2 to 8, characterized in that the conversion of the natural extract into a water-alcohol solution is carried out in a second solvent system comprising or even consisting of at least one solvent from the first solvent system.

11. Process according to any one of claims 2 to 10, characterized in that the conversion is carried out directly on the basis of an oil or butter-rich organic solution, in particular comprising at least 2% by weight, in particular at least 5% by weight, or even at least 10% by weight, of oil or butter relative to the total weight of the oil or butter-rich organic solution.

12. The method according to claim 11, characterized in that the conversion is carried out on a distillate fraction, in particular a partially evaporated distillate fraction, to which less than 50 wt. -% of other solvents are added, or even no other solvents are added.

13. Process according to any one of claims 2 to 12, characterized in that the extraction of the hydro-alcoholic solution is carried out by liquid/liquid extraction using a third solvent system comprising all or part of the same solvent as the user in the first and/or second solvent system.

14. Process according to any one of claims 1 to 13, characterized in that the unsaponifiable matter obtained is chosen from soybean unsaponifiables, avocado unsaponifiables, in particular avocado unsaponifiables rich in furan-type fractions and/or avocado unsaponifiables rich in sterol-type fractions, and more particularly mixtures of Avocado and Soybean Unsaponifiables (ASU).

15. An oil or butter or unsaponifiable fraction free of solvents classified in the list of UE1, UE2 and/or US CMR, said fraction or said oil or said butter being suitable for being obtained by the method according to any one of claims 1 to 14, in particular said oil or fraction being obtained by the extraction method according to any one of claims 1 to 14.

16. Use of HMDS in a content ranging from 0.1 to 49% by volume relative to the total volume of the extraction solvent in a solid/liquid extraction process, advantageously for the solid/liquid extraction from plant solid materials or microorganisms.