FR3055555A1 - METHOD OF EXTRACTING PRODUCTS VALORIZABLE FROM ORGANIC RESIDUES AND WASTE FROM VINE, VINIFICATION AND AGING OF WINE, AND APPARATUS FOR IMPLEMENTING SAID PROCESS - Google Patents

Abstract

The present invention relates to a process for extracting recoverable products from residues and / or organic waste from the vine, vinification and aging of the wine, characterized in that the said residues and / or organic wastes are subjected to extraction with water in a subcritical state (ESC), then recovering the extract obtained.

Description

© Publication no .: 3,055,555 (to be used only for reproduction orders)

©) National registration number: 16 58202 ® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY

COURBEVOIE © IntCI ⁸

B 01 D 11/04 (2017.01), B 01 J 16/00

A1 PATENT APPLICATION

©) Date of filing: 02.09.16. © Applicant (s): VERT PROCESS— FR. ©) Priority: @ Inventor (s): BILLARD ROMEAN. ©) Date of availability of the request: 09.03.18 Bulletin 18/10. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ® Holder (s): PROCESS GREEN. ©) Extension request (s): Polynesia-Fr ® Agent (s): CHAILLOT GENEVIEVE.

104 / PROCESS FOR THE EXTRACTION OF RECOVERABLE PRODUCTS FROM ORGANIC RESIDUES AND WASTE FROM THE VINE, VINIFICATION AND AGING OF WINE, AND APPARATUS FOR CARRYING OUT THIS PROCESS.

©) The present invention relates to a process for extracting recoverable products from organic residues and / or waste from the vine, from vinification and from aging of the wine, characterized in that said residues and / or organic waste on extraction with water in a critical state (ESC), then that one

FR 3 055 555 - A1

PROCESS FOR THE EXTRACTION OF RECOVERABLE PRODUCTS FROM

ORGANIC RESIDUES AND WASTE FROM THE VINE, VINIFICATION AND AGING OF WINE, AND APPARATUS

FOR THE IMPLEMENTATION OF THIS PROCESS

The present invention relates to a process for extracting recoverable products from organic residue and waste from the vine (Vitis vinifera), from vinification and aging of wine.

The extracts obtained contain compounds with high added value for various applications, in particular for the cosmetic, pharmaceutical, food and wine industries.

The vine and wine sector produces grapes, viticulture by-products: vine leaves, tendrils, stems, vine shoots and stumps, and vinification by-products which, for white wine, are the stems from the destemming operation, the muds from the fulling and decantation or sedimentation operation, and the lees from the fermentation and aging operations, and, for red wine, are the marc from the 'devatting and pressing operation, lees from aging operations, used shavings and old barrels also from vinification and aging operations.

• The roundup is the inflorescence of the bunch of grapes. It is therefore branched. The longest branch forms the main axis of the inflorescence. At maturity, it represents 3 to 6% of the weight of the ripe bunch. The roundup is low in sugars but rich in phenolic compounds. It can contain up to 20% of the total phenolic compounds of the frame of a bottle, is the use of the cluster while it represents a lower proportion by weight. The highest concentrations of transresveratrol are detected in the roundups. The main molecules identified are resveratrol and its main oligomers, as well as catechins.

• The grape marc is obtained after the separation of the solid parts from the liquid following the first alcoholic fermentation. A significant amount of juice (about 6 to 13% of the total volume) is contained in this residue. The marc consists of dandruff, seeds and a tiny part of plant debris. It thus contains all the phenolic compounds present in the entire composition of the grape berry. It is the most complete co-product in terms of aromatic and flavonoid substances. The main molecules identified are trans and cis resveratrol, catechins, anthocyanidins and proanthocyanidins.

• Traditionally, the aging of great wines, from the end of the vinification to the setting in oak barrels.

the barrel promotes color stabilization reactions, the softening of the tannins by modifying the structures of the phenolic compounds and the development of the aromas, compared to the sealed tank and in principle inert towards the wine. Finally, the wine acquires a complexity linked to the odorous substances extracted from the wood. The matrix structure of wood not only provides gentle oxygenation but also gives it a great diversity of polarity of compounds such as sugars, acids, steroids, hydroxylable tannins, terpenes, phenols and lactones.

Some of these vitivinicultural by-products are taken up, transformed and recycled by distilleries.

However, this recycling system alone does not allow the correct recovery of all of these by-products of interest from these wine-growing by-products. This recovery is an essential issue at present and aims at the recovery, at low cost or at low cost, of compounds with high added value.

Traditional extraction techniques used methods of infusion, decoction or maceration. Then the use of chemical solvents made it possible to improve yields quantitatively and qualitatively. However, these extraction methods are still too expensive due to the use of huge quantities of necessary solvent, solvent sometimes having a low selectivity for the compounds to be extracted. In addition, the use of solvent for the treatment of plant materials is subject to increasingly strong restrictions, in particular since the implementation of the REACH directive (regulation on registration, evaluation, authorization and chemical restrictions), aimed at ensuring a high level of protection of human health and the environment from the risks that these chemicals may pose. These restrictions are particularly important in the food industry, for which it is becoming urgent to offer alternative substances to the organic solvents traditionally used in the extraction or purification processes of plant material.

The Depositing Company has discovered that recoverable products can be obtained by subcritical water extraction, a process which respects the natural origin of the by-products of winemaking, such as stalks, marc, shavings and barrels, without use. solvent, with good species selectivity with shorter extraction times compared to solvent extraction processes.

The products extracted by the process of the invention are mainly phenolic compounds. Phenols have an important role on the organoleptic properties of wine (color, astringency, bitterness ...) and provide interesting nutritional and pharmacological properties (vitamin, bactericidal, antioxidant) which can protect the consumer from cardio- vascular, neuronal disorders, cancer, diabetes and obesity, etc.

Phenolic compounds are secondary metabolites of plants which are characterized by one or more benzene nuclei carrying one or more hydroxyls and are generally present in the form of an ester or heteroside.

Among these compounds are nonflavonoids, such as acid-phenols and stilbenes; flavonoids, such as anthocyanins, flavanols, flavonols and flavonolols.

• Among the phenolic acids, seven benzoic acids of the wine formula:

have been identified in

RI = R2 = R3 = R4 = H: p-hydroxybenzoic acid

RI = H, R2 = R3 = OH, R4 = H: protocatechic acid

RI = H, R2 = R3 = OCH3, R4 = H: vanillic acid

RI = H, R2 = R3 = R4 = OH: gallic acid

RI = H, R2 = R3 = R4 = OCH ₃ : syringic acid

Rl = OH, R2 = R3 = R4 = H: salicylic acid

RI = OH, R2 = R3 = H, R4 = OH: gentisic acid

The most common forms are gallic and vanillic acids (from wood, enriched during aging).

Other acid-phenols belonging to the series of cinnamic acids of formula

RP D1 z ni

CH - CH — COOH

and R2 the { wine under f orrr 1 ' acid tartaric or d RI = R2 = R3 = R4 = H RI = H, R2 = R3 = OH, RI = H, R2 = R3 = och _3i RI = H, R2 = R3 = R4 =

are present in the grape

In hydroalcoholic medium, the phenol acids are colorless, but they can take a yellow color after oxidation (browning). The concentration of these compounds in red wine is around 100 to 200 mg.L ^-1 and in white wine it is 10 to 20 mg.L ^{_ ±} . These compounds are mainly extracted from the skin of the grapes under the action of heat in red wine making.

-i formula

The stilbenes of

R

(trans and cis isomers, respectively) are polyphenols, the basic skeleton of which consists of two benzene rings linked by an ethylene bridge. From this relatively simple structure, there is a large variety of compounds, the nature of which varies according to the number and the position of the hydroxyl groups, the substitution by sugars or methoxy residues, as well as the steric configuration ( trans and cis) of the molecule:

RI = R2 = R3 = OH, R4 = H: trans- or cis-resveratrol RI = R2 = OCH3, R3 = OH, R4 = H: pterostilbene (trans)

RI = 0-Glc, R2 = R3 = OH, R4 = H: trans- or cis-picideide RI = R2 = OH, R3 = 0-Glc, R4 = H: trans- or cisververroloside

RI = R2 = R3 = R4 = OH: trans-piceatarnol or O-Glc = Dglucose

Rl = 0-Glc, R2 = R3 = R4 = OH: trans-astringine

The trans- and cis- isomers of resveratrol and their glucosides, trans- and cis-picideides, constitute the four stilbenes most conventionally present in wine and the vine.

Flavonoids are characterized by the phenyl-2-benzo-pyran nucleus of formula

consisting of two benzene nuclei linked together by a heterocycle:

a) R3 = OH, R'3 = R'5 = H: kaempferol R3 = OH, R'3 = OH, R'5 = H: quercetin R3 = OH, R'3 = R'5 = OH: myricetin b) R3 = OH, R'3 = OH, R'5 = H: dihydroquercetin

(taxifoline)

This family includes several groups: the most represented are anthocyanins, flavonols and flavanols, most often in the form of glucoside.

Anthocyanins are poly / hydroxy derivatives of benzopyrilium (flavylium) salt of formula

which can be present in different chemical forms in plant tissues:

RI = OH, R2 = H: cyanidine

RI = OCH3, R2 = H: paéonidine RI = R2 = OCH3: malvidine RI = R2 = OH: delphinidine RI = OCH3, R2 = OH: petunidine

At acid pH, the predominant form is the flavylium cation (red in aqueous solution), while at higher pH, this favylium cation is converted into other species, some of which are colorless. More than fifteen anthocyanins have been identified in grape berries including 5 most common anthocyanidins: cyanidin, delphinidin, petunidin, paeonidin, and malvidin.

• Anthocyanidins are in the form of 3-0monoglucosides and can be esterified by different acids (acetic, coumaric and caffeic) at the level of C6 of glucopyranose, with very great disparities from one grape variety to another. Anthocyanins are mainly found in the skin of the berry.

In wine, the 3-0-monoglucoside forms are the most represented (200 to 800 mg / L), with a frequent predominance for malvidine-3-Ο-βglucoside. Paleonidine-O-p-glucoside shows fairly marked differences in content. It is predominant in certain grape varieties as in the pulp of the berries of certain dye grape varieties such as Dunkelfelder or blue Portuguese. These molecules participate in the color of red wines, which varies during the aging of the wine (condensation and reduction of free anthocyanins as the complexes progress, T — T (tannin-tannin); T — A (tannin-anthocyanin); A— A (anthocyanin-anthocyanin); T — E — A (tannin-ethanolanthocyanin), formed).

• The catechins flavanols represented by and (-) - epicatechin) monomers ((+) of formula

OH

R * (catechin series)

R '= R' '= H: (+) - catechin (2R, 3S)

R '= R' '= H: (-) - catechin (2S, 3R)

R '= OH, R' '= H: gallocatechin

R '= H, R' '= gallic acid: galloylated catechin or of formula

R '= R' '= H

R '= R' '= H:

(epicatechin series) (+) - epicatechin (2R, 3S) (-) - epicatechin (2S, 3R) galloylated epicatechin as oligomers,

R '= OH, R' '= H: epigallocatechin R' = H, R '' = gallic acid:

(epicatechin-3-0-gallate), commonly known as catechic tannins.

These molecules are involved, to a large extent, in the taste properties of wines. In red wines, catechin is present at concentrations ranging from 150 to 220 mg.Lh ¹ , while in white wines the content is much lower, of the order of 40 mg.Lh ¹ . Epicatechin is also present at lower concentrations (80 mg.Lh ¹ ).

The oligomers are formed by the condensation of flavan-3-ol units linked together by interflavanic bonds of the C4-C8 or C4-C6 type. Among them, four dimers have been highlighted in red wines. In wines, they are found at average concentrations of 2 70 mg.L ^-1 .

The parts of the plant that contain the most catechins are the seeds, from which they are extracted ίο during winemaking. The oligomers are present in the film and the seeds.

Flavonols are yellow tint pigments

of formula '“' ^{ri w} which are present in grapes of all varieties:

RI = H, R2 = R3 = OH: quercetin

RI = H, R2 = OH, R3 = 0-Glc: quercitrin

RI = R2 = R3 = OH: myricetin

RI = R 2 = H, R3 = kaempferol

RI = H, R2 = OH, R3 = 0-Glc-Rha: rutin

In wine, these molecules generally exist in the form of aglycone, the main ones being quercetin and myricetin, in small quantities (4 to 16 mg.L ^-1 and 5 to 13 mg.L ^-1 respectively) and kaempferol . In grape juice, quercetin is found at levels of 9 mg.L_ ^x . Some heterosides of quercetin are also present in red wine, such as rutin (quercetin 3Ο-β-rutonoside) at levels of 9 mg.L ^-1 , quercitrine (quercetin 3-0-3-glucoside) and isoquercitrine (quercetin 3-0-p-rhamnoside).

Flavanolols (dihydroflavonols) of formula

π

RI = H: dihydroquercetol

RI = OH: dihydromyricetol are the main compounds identified in grapes and wine.

Astilbin (dihydroquercetol-3-O-rhamnoside), already described in white wines, has been isolated from the must and stems of Vitis vinifera.

The present invention therefore relates to a process for extracting recoverable products from organic residues and / or waste from the vine, from vinification and from aging of the wine, characterized in that said residues and / or organic waste on extraction with water in a critical state (ESC), then recovering the extract obtained.

Residues and / or organic waste from the vine are chosen from vine leaves, tendrils, stalks, vine shoots and stumps; those for winemaking are chosen from muds, shavings, marc, lees; and those of the aging of the wine come from barrels, barrels and old barrels.

Said organic residues and / or wastes can be subjected, when they are in the solid state, to grinding, in particular up to a particle size of 0.5 mm to 2 mm, preferably from 0.5 mm to 1 mm, before subjecting them to extraction.

The extraction can be carried out with water in the subcritical state at a temperature between 100 ° C and 374 ° C and under a pressure between 0.1 MPa (1 bar)

and 19,565 MPa (195.65 bar), in particular to a temperature between 120 and 150 ° C and below a pressure between 0.207 MPa (2, 07 bar) and 0.506 MPa

(5.06 bar).

The superior mass transfer property of ESC leads to high diffusivity and therefore greater extraction efficiency. The solubility and diffusivity of water at moderate pressure is therefore comparable with organic solvents.

Residues and / or organic waste can be subjected to at least one extraction operation, in particular one to four extraction operations, by each time passing water in a liquid state under criticism through a mass of residues and / or organic waste.

It is thus possible to pass at least once, in particular one to four times, liquid water in the subcritical state through samples of organic vine residues contained in a hydrobaric hydrothermal container or reactor, the latter being filled to 70 to 80%, in particular to 80% in internal volume to take into account the expansion (swelling rate) of the organic residue samples when the water passes to the subcritical state. The speed of passage can be from 2 to 6 ml of sample per minute, in particular from 2 to 3 ml of sample per minute.

An aqueous extract can be recovered which is cooled for collection, said extract being able to be filtered before or after cooling.

We can recover the stalks at the destemming or destemming stage where they are separated from the berries at the entrance of the cellar before the vatting during vinification

for obtaining white wine, or the destemming stage partial during a winemaking for obtaining wine red. In the case of roundups, we can recover a extract containing flavanols, flavonols, of dihydroflavonols and stilbenes, in particular the

quercetin 3-O-glucorondin, quercetin 3-O-rutinoside, ε-Viniferin, trans-resveratrol and α-Viniferin.

In the case of marc, anthocyanins and tannins can be recovered, in particular peonidine-3-0glucoside, malvidine-3-0-glucoside, malvidine-3-0-pcoumaroyleglucoside, catechin, epicatechin and l 'gallic acid.

The present invention also relates to an apparatus for implementing the above method, characterized in that it comprises at least one reactor capable of receiving the organic residues and / or waste to be extracted, said reactor or said reactors being supplied (s) in water which comes from a reservoir and which is made to pass into the subcritical state for its entry into said reactor (s), a cooling device positioned at the outlet of said reactor (s) and a tank of recovery of the extract;

a depressurization member which can be arranged at the outlet of said reactor or reactors;

a filtration device which can be positioned at the outlet of said reactor or reactors upstream of the cooling device or downstream of it for the filtration of said crude extract obtained at the outlet of said reactor or before it is collected in said recovery tank;

a recycling conduit capable of bringing water back to the subcritical state charged with extract at the outlet of said reactor or reactors to a point situated upstream of it or of these to form a closed circuit for at least one new passage through the residues and / or organic waste to be extracted.

Advantageously, two reactors can be mounted in parallel, one being in service for extraction while the other is out of service for extraction and is then drained, cleaned and refilled, in order to conduct the extraction of continuously.

Part of the water in the feed water tank can form the cooling circuit of the cooling device before it is recycled into said feed water tank.

The advantages of this extraction process are that at the end of the process, 100% natural extracts are obtained, without any trace of solvent and given the low pressure (0.1 MPa to 19.565 MPa) associated with the temperature allowing liquid phase extraction, all of the compounds, from matrices as complex as wood, could be dissolved and extracted. Also, this process allows short extraction times, selectivity and high yield. In addition, the therapeutic properties of the final product extracted by subcritical water extraction are very close to those of the crude product. Sub-critical water extraction is therefore currently the most ecological and technological means of obtaining very high quality plant active ingredients. The use of water as an extraction solvent meets the requirements of an eco-innovative green process.

We will now describe two types of apparatus for implementing the method according to the invention with reference to the accompanying drawing.

In this drawing, FIGS. 1 and 2 schematically represent an apparatus for extracting sub-critical water by organic residue and waste from the vineyard, from the vinification and from aging of the wine in a batch mode and in a continued.

An apparatus for implementing an extraction method according to the invention in a batch mode will now be described with reference to Figure 1 of the accompanying drawing.

This apparatus includes an autoclave 1 (or extraction cell) in which is placed a reactor 2 made of stainless steel, of cylindrical shape, intended to contain a batch 3 of residues from the vine, the vinification or the aging of the wine to be subjected. at the extraction. The autoclave 1 is crossed at its upper part by a conduit 4 which brings water from a reservoir 5 and on the path of which are successively disposed a pump 6 (HPLC pump) and a pressure gauge 7.

The conduit 4 is extended in the autoclave 1 by a vertical branch 4a then branches off into a horizontal branch 4b to go up, by a shorter vertical branch 4c, to the bottom of the reactor 2, where it delivers the water, which is forced upwards through batch 3 of residues intended to be subjected to extraction.

The water circulating in the branches 4a, 4b and 4c is heated by a heating resistor 8 entering the autoclave 1 and plunging into the branch 4a. The temperature of the water in the autoclave 1 is regulated by the temperature regulator 9. A sheath 10 surrounds the branches 4a, 4b to maintain the desired temperature of the water during its passage through the reactor 2.

The heated and pressurized water rises through the batch 3 to exit to the upper part of the reactor 2 in the form of an extract via a conduit 11 which comprises, externally to the autoclave 1, a first horizontal branch 11a, then descends by a U-shaped part 11b, then a horizontal branch linked and finally by a vertical descending branch lld.

The lower region of the U-shaped part 11b is immersed in a cooling bath 12 in which there is a cooling coil 13.

On the branch 11c is disposed a pressure regulator 14 which is a valve type valve and, downstream thereof, a pressure gauge 15 which indicates the pressure at the outlet.

The end of the lld branch plunges into a container 16 for the recovery of extract 17.

The pressurization of the water is therefore ensured by the pump 6 and the valve type valve 14 at the outlet which is closed so as to reach the desired pressure.

The autoclave 1 is such that it makes it possible to create a system isolated from the external environment in which the set temperature is maintained by the resistor 8.

To operate the apparatus of Figure 1, the following successive steps are carried out:

- the thermoregulator 9 is turned on and the desired temperature is set;

- the pressure control valve 14 is closed;

- when the measured temperature has reached the set temperature, pump 6 is started and adjusted to the desired flow; the display of pump 6 is switched to "P total" to monitor the pressure at the inlet of reactor 2;

- when the pressure is at 20 bar on the pressure gauge, the desired pressure is adjusted by gently opening the pressure regulation valve 14;

- the extract is harvested when the system air is completely evacuated;

- the pressure is maintained at the desired value using the regulating valve 14.

To stop and clean the system, proceed as follows:

- once the extract has been collected, a waste container is placed in place of the collection container 16 and the control valve 14 is opened. The thermoregulator 9, the autoclave 1 are turned off (the switch is switched to "with timer ”) and pump 6 is stopped;

- The purge valve of the pump 6 is opened and it is closed once all the pressure has been released;

- the reactor 2 is taken out, the wearing of anti-heat gloves is compulsory under risk of burns. A washing cable is put in place;

- the system is washed with 200 mL of 70% EtOH at a rate of 5 mL / min. If this is the last extraction, the system is left under EtOH at 70%. Otherwise, the system is rinsed with 200 mL of H ₂ O at the rate of 5 mL / min;

- the pump is stopped and turned off. Vacuum and wash the reactor 2, then rinse with EtOH.

If we refer to Figure 2 of the accompanying drawing, we can see that there is shown an apparatus for carrying out the extraction according to the invention continuously.

This apparatus comprises two identical reactors 101A, 101B, which are intended to be in turn in service.

These reactors 101A, 101B are of cylindrical shape, made of stainless steel, thermally insulated, and each contain a basket 102A, 102B intended to receive the plant material to be subjected to extraction.

The reactors 101A and 101B are joined, at their upper part, by a conduit 103 on the path of which is a three-way solenoid valve 104, and, at their lower part, by a conduit 105 on the path of which is a solenoid valve with three-way 106.

Above the lower closing plate of each reactor 101A, 101B, is disposed a sintered disc or a sintered membrane, respectively 107A, 107B, which lets the water and the solute which it contains pass through, retaining the plant material.

Below the upper closing plate of each reactor 101A, 101B, is disposed a sintered disc or a sintered membrane respectively 107C, 107D allowing the water entering the reactor 101A, 101B respectively to pass.

Rainwater, drilling or drinking water contained in a tank 108 is brought to the solenoid valve 104 to be brought in turn to the upper part of each of the reactors 101A, 101B by a conduit 109 on the path of which are arranged. successively:

- a supply solenoid valve 110;

- a centrifugal pump 111;

- A heating plate exchanger 112, which is intended to heat the water arriving at each of the reactors 101A, 101B;

- a flow transmitter 113, which measures and transmits the flow to the regulation and makes it possible to identify the limit pressure drop;

- a transmitter pressure gauge 114, which measures and transmits the pressure of the circuit to the regulation.

The oil circuit on which there is a heater 116 is shown at 115, which heats the oil in a closed circuit to a high temperature, for example

200 ° C, to transmit heat to the water contained in conduit 109.

The water charged with the materials extracted in each of the reactors 101A, 101B is sent, from the solenoid valve 106, to a cooled collecting tank 117 by a conduit 118, on the path of which there are successively:

a solenoid valve 119 for draining and depressurizing, which is open when the solenoid valve 104 is closed;

- a cooler plate exchanger 120; and

- a membrane filter 121 for concentrating the extracted material.

In the cooled collection tank 117, the extract can be stored for example at a temperature of + 4 ° C. In FIG. 2, the cooling group has been designated by the reference numeral 122.

The exchanger 120 receives the cooling water coming from the reservoir 108 through the conduit 123 on the path of which is disposed a circulation pump 124.

The cooling water which has heated up in the exchanger 120 is recycled through the line 125 into the tank 108.

Part of the water containing the extracted substances can be recycled from the solenoid valve 119, through the conduit 126, into the conduit 109 between the supply solenoid valve 110 and the pump 111. On this conduit 126, there is a solenoid valve 127 which is open when the solenoid valve 110 is closed, allowing a loop circulation of the water for the extraction.

In Figure 2, there is also shown a worm pump 128 which conveys the plant material, via line 129, into the reactor 101B, knowing that it will in turn route said plant material to the reactor 101A.

Also included in 130 was the computer for controlling and piloting the apparatus.

The operation of the apparatus shown in Figure 2 is as follows:

The reactor 101A is filled with the material to be extracted or matrix to a part of its internal volume (for example to 80% of its internal volume) to take account of the swelling of this material by the extraction water.

Is brought to the reactor 101A thus filled with water from the reservoir 108, the water being pressurized by the pump 111 and being heated in the plate exchanger 112. The pressure and the temperature are chosen so that the water is in a subscribed state, which is an "induced" state where the water oscillates permanently between a gaseous state and a liquid state. The water then behaves like an organic solvent because its dielectric constant drops from 78.5 to approximately 27. We then observe a decrease in surface tension, an ease of penetrating into the core of the matrices to be extracted, greater selectivity and high yield of solutes and concentrates (for example rich in polyphenols) extracted from the matrix in a relatively short extraction time.

The water in the subcritical state arrives in the reactor 101A by the upper part thereof, the reactor 101A defining a hermetically sealed extraction medium thanks to the sintered discs or sintered membranes 107A, 107C. As indicated above, the upper sintered disc 107C allows the arrival of the water in the subcritical state and the lower sintered disc 107A allows the diffusion and the flow of the water and of the solutes extracted by percolation, that is to say by the passage of water in the subcritical state through the matrix which becomes more permeable.

The water and the solutes extracted are sent to the collecting tank 117 by the conduit 118 after depressurization by the solenoid valve 119, cooling in 120 and filtration through the membrane filter 121.

However, it is possible to pass several times through the matrix contained in the reactor 101A the water with its extracts which leaves the reactor 101A by closing the solenoid valve 119 so as to reinject the outgoing water into the conduit 109, the solenoid valve 110 being closed and the solenoid valve 127 being open. A water more concentrated in the desired extracts is then obtained at the outlet, which is recovered as before by reopening the solenoid valve 119.

When the matrix contained in the reactor 101A is exhausted, one acts on the three-way solenoid valves 104 and 118 to cut the supply of the reactor 101A and isolate it and to put into service the reactor 101B which then functions for the extraction in the same way as the reactor 101A.

During this time, the reactor 101A is drained, disinfected and re-filled with fresh matrix so as to be ready to be put into service when the matrix being extracted contained in the reactor 101B is exhausted.

Examples

The following examples illustrate the present invention without, however, limiting its scope.

A - General operating mode of the process in batch mode (see Figure 1)

Al - Sample preparation

The fragmented wood samples were reduced in size according to the grain size using a household appliance, a traditional kitchen mixer and a sieve.

The stalks and wood samples (chips or barrels) are gathered into three homogeneous lots, named Gl, G2 and G3 respectively according to the particle size of the samples:

Gl> 2 mm mm <G2 <1 mm

G3 <1 mm

A2 - Subcritical extraction g of the sample were placed in the tank 2. The latter was then installed in the extraction enclosure 1. Then the extraction temperature T was determined. The pressure regulator 14 at the outlet of enclosure 1 was systematically closed before pressurization with a constant flow speed. The water flow rate was adjusted to 2 mL / min. The extraction temperatures T tested were 100 ° C, 125 ° C, 150 ° C, 175 ° C, 200 ° C and 250 ° C and were compared with the extractions at 60 ° C and 80 ° C. The constant pressure was set at 5 MPa (50 bar). The cooled solution was collected in container 16 and was then stored at + 4 ° C for the rest of the process.

For each batch of sample treated, a total of 200 mL of extract was collected in a loop of 4 extraction cycles. The first cycle corresponds to the first fraction of 50 ml obtained, the second to the second fraction, the third to the third fraction, and finally the fourth and last extraction cycle to the last fraction of 50 ml. Each cycle lasted 25 minutes of extraction and the amount collected for each was 50 mL.

A3 -Results and analyzes

In order to observe the differences in concentrations of phenolic compounds and to determine which conditions favored the best polyphenolic enrichment, the analysis of the Total Polyphenol Index (TPI) was carried out on each of the samples. The IPT provides a general idea of the content of phenolic compounds present in the extracts.

The extract is diluted 100 times and the optical density is measured at 280 nm relative to distilled water under 1 cm of optical path in a UV-permeable tank (quartz). The result is expressed by an index with I = DO x dilution.

The IPT measurements were carried out with a PerkinElmer Lambda 25 spectrophotometer.

In examples 1 to 3, the samples are named x.l, x.2, x.3 and x.4 according to the number of extraction cycles carried out.

Example 1 - Extraction from samples of roundups (sub-critical extraction process)

For ESC extracts, the pH is generally above 5 and demonstrates the presence of chemical compounds such as polyphenols, aromatic stilbenes, anthocyanins and condensed tannins.

Table 1 shows the process conditions, the IPT and the products extracted by the process.

Table 1 - Summary of the IPT and the products extracted from roundup samples as a function of temperature, pressure and particle size conditions

Sample Temperature (° C) P (bar) Granulometry PH IPT Products extracts 1.1 175 50 1 5.15 192.5 aa * ttp ** vitamin E stilbenes and catechins 1.2 4.52 94.9 1.3 3.89 34.0 1.4 3.79 21.2 2.1 150 50 2 5.20 170.1 aa * ttp ** vitamin E stilbenes and catechins 2.2 4.93 83.2 2.3 4.32 35.4 2.4 3.89 17.85 3.1 125 50 2 5.20 252.8 aa * ttp ** vitamin E stilbenes and catechins 3.2 4.93 62.6 3.3 4.32 28.35 3.4 3.89 18.4 4.1 125 50 1 5.15 60.1 aa * ttp ** vitamin E stilbenes and catechins 4.2. 4.94 50.65 4.3 4.57 25.2 4.4 4.26 40.0 5.1 175 50 Raw extract 5.23 101.5 aa * ttp ** vitamin E stilbenes and catechins 5.2 5.14 91.4 5.3 4.93 48.6 5.4 4.65 23.6 6.1 125 50 Raw extract 5.12 60.4 aa * ttp ** vitamin E stilbenes and catechins

6.2 4.77 61.7 6.3 4.13 45.45 6.4 4.65 28.7 7.1 150 50 Raw extract 5.13 170.4 aa * ttp ** vitamin E stilbenes and catechins 7.2 5.14 92.4 7.3 4.82 26.6 7.4 4.47 48.85 8.1 210 50 4.87 293.2 Destructuring of the matrix and oxidation of the compounds 8.2 4.27 173.7 8.3 3.81 65.25 8.4 3.78 29.65 9.1 100 5.29 84.6 Concentration too low to determine 9.2 5.06 72.2 9.3 4.75 49.6 9.4 4.46 25.0 10.1 80 50 5.20 96.9 Concentration too low to determine 10.2 5.08 91.2 10.3 4.75 53.8 10.4 4.45 28.4 11.1 60 50 5.65 146.5 Concentration too low to determine 11.2 4.96 89.2 11.3 4.82 39.1 11.4 4.74 19.7 12.1 150 50 2 4.76 286.6 aa * ttp ** vitamin E stilbenes and catechins 12.2 4.40 121.0 12.3 4.10 67.2 12.4 4.02 48.6 13.1 225 50 2 4.41 379.8 Destructuring of the matrix and oxidation of the compounds 13.2 4.02 186.9 14.1 175 50 1 93.5 Start destructuring because grain size is small

14.2 79.4 14.3 43.3 14.4 29.5 15.1 175 50 Raw extract 82.8 aa * ttp ** vitamin E stilbenes and catechins 15.2 20.1 15.3 52.8 15.4 29.6

★ Amino acid; ★★ Tryptophan

The main molecules identified belong to the family of flavanols, flavonols, dihydroflavonols and stilbenes. The roundup matrix has the singularity of containing stilbenic metabolites and dihydroflavonols. They are flavonoids of the flavonol type, derived from myricetin and quercetin, which are powerful antioxidants. The main molecules observed are: Quercetin 3-0glucorondin, Quercetin 3-O-rutinoside (rutin), ε-Viniferin, trans-resveratrol and α-Viniferin.

Example 2 - Extraction from marc samples (subcritical extraction process)

The procedure was as in Example 1 except that the extraction is carried out from marc samples and that there was no grinding step.

In Table 2, the process conditions, the IPT and the products extracted by the process are shown.

Table 2 - Summary of 1ΊΡΤ and products extracted from marc samples depending on temperature and pressure conditions

Sample Temperature (° C) P (bar) IPT Products extracts 1.1 125 50 90.2 Anthocyanins and tannins 1.2 85.9 1.3 79.0 1.4 62.2 2.1 150 50 110.1 Anthocyanins and tannins 2.2 107.2 2.3 71.4 2.4 59.85 3.1 175 50 220.8 Anthocyanins and tannins 3.2 211.6 3.3 197.35 3.4 167.4 4.1 200 50 150.1 Anthocyanins and tannins 4.2. 139.65 4.3 125.2 4.4 98.0

Among the compounds extracted from marc samples, anthocyanins have been identified (peonidine-3-0-glucoside, malvidine-3-0-glucoside, malvidine-3-0-p-coumaroyleglucoside) and tannins (catechin, epicatechin , gallic acid).

Example 3 Extraction from Chip Samples (Subcritical Extraction Process)

The procedure was as in Example 1 except that the extraction is carried out from chip samples.

In Table 3, there are process conditions and IPT.

For chip extracts by ESC the initial pH is around fact (and.

figure the barrels)

Table 3 - Summary of 1ΊΡΤ detected from chip samples as a function of temperature, pressure and particle size conditions

Sample Temperature (° C) P (bar) Granulometry PH IPT 1.1 175 50 2 4.12 162 1.2 3.21 82.9 1.3 2.76 53.7 1.4 2.73 33.1 2.1 200 50 2 3.73 213.4 2.2 2.97 119.5 2.3 2.95 80.5 2.4 3.04 62.9 3.1 150 50 2 4.07 173.3 3.2 3.42 59.2 3.3 3.42 59.9 3.4 3.04 40.1 4.1 125 50 2 4.05 165.9 4.2 4.02 90 4.3 3.39 53.8 4.4 2.90 38.2 5.1 200 50 1 3.68 239.6 5.2 2.89 268.6 5.3 2.89 95.6 5.4 2.74 87 6.1 175 50 1 3.82 268.6 6.2 3.02 268.6 6.3 2.76 90.3 6.4 3.06 74.7

B - General operating mode of the process in continuous mode (see Figure 2)

Bl - Preparation of samples

The shavings, stalks, branches, old barrels are fragmented and reduced in size according to the grain size using a knife grinder. Solids such as cobs or chips can be dried with hot air before crushing.

Wet residues (marc, lees, muds) are preconcentrated according to their variable humidity level according to grape variety, vintage, oenological practice, etc. before extraction.

B2 - Subcritical extraction

During each extraction, the raw material must be carefully weighed before filling the reactor. Then the predetermined extraction temperature must be set. The extraction cell outlet valve is systematically closed before pressurizing with a constant flow speed. The water flow rate was adjusted to 0.19 L / min. The recommended extraction temperature is 150 ° C. The constant pressure is 0.506 MPa. The solution should be collected after cooling and stored at + 4 ° C for further analysis.

Operating parameters:

Volume to be extracted: 35 L

Bulk density of the raw material: 0.27

Solvent level: 7.14

Amount of material: 9.45 kg

Water requirement: 67,473 L

Q = 0.19 L / min or 11.24 L / hour

Extraction temperature: 150 ° C for 0.506 MPa

Claims (10)

1 - Process for the extraction of recoverable products from organic residues and / or waste from the vine, from vinification and from aging of the wine, characterized in that said residues and / or organic waste are subjected to extraction with water in a critical state (ESC), then recover the extract obtained. 2 - Process according to claim 1, characterized in that the residues and / or organic waste from the vine are chosen from vine leaves, tendrils, stalks, vine shoots and vine stumps; those for winemaking are chosen from muds, shavings, marc, lees; and those of the aging of the wine come from barrels, barrels and old barrels. 3 - Method according to one of claims 1 or 2, characterized in that said residues and / or organic waste, when these are in the solid state, are subjected to grinding, in particular to a particle size from 0.5 mm to 2 mm, preferably from 0.5 mm to 1 mm, before subjecting them to extraction. 4 - Method according to one of claims 1 to 3, characterized in that one carries out the extraction with water in the subcritical state at a temperature between 100 ° C and 374 ° C and under a pressure between 0.1 MPa and 19.565 MPa, in particular at a temperature between 120 and 150 ° C and under a pressure between 0.207 MPa and 0.506 MPa. 5 - Method according to one of claims 1 to 4, characterized in that the organic residues and / or wastes are subjected to at least one extraction operation, in particular one to four extraction operations, by passing each time water in a critical liquid state through a mass of organic residues and / or waste. 6 - Method according to one of claims 1 to 5, characterized in that an aqueous extract is recovered which is cooled for collection, said extract can be filtered before or after cooling. 7 - Method according to one of claims 1 to 6, characterized in that, in the case of roundups, an extract is recovered containing flavanols, flavonols, dihydroflavonols and stilbenes, in particular quercetin 3-0- glucorondin, quercetin 3-0-rutinoside, ε-Viniférine, trans-resveratrol and a-Viniférine, and, in the case of marc, anthocyanins and tannins are recovered, in particular peonidine-3-0 -glucoside, malvidine-3-0-glucoside, malvidine-3-0-pcoumaroyleglucoside, catechin, epicatechin and gallic acid. 8 - Apparatus for implementing the method according to one of claims 1 to 7, characterized in that it comprises at least one reactor (101A; 101B) capable of receiving the residues and / or organic waste to be extracted, said one or more reactors (101A; 101B) being supplied with water which comes from a reservoir (108) and which is passed to the sub-critical state for its entry into said one or more reactors (101A ; 101B), a cooling device (120) positioned at the outlet of said one or more reactors (101A; 101B) and a tank for recovering the extract; a depressurization member (119) which can be disposed at the outlet of said reactor or reactors (101A; 101B); a filtration device (121) which can be positioned at the outlet of said reactor (s) (101A; 101B) upstream of the cooling device (120) or downstream thereof for the filtration of said crude extract obtained at the outlet of said reactor (s) (101A ; 101B) before its collection in said recovery tank (117); a recycling conduit (126) capable of bringing water back to the subcritical state charged with extract at the outlet of said reactor or reactors (101A; 101B) at a point situated upstream thereof or thereof to constitute a closed circuit for at least one new passage through the residues and / or organic waste to be extracted. 9 - Apparatus according to claim 8, characterized in that two reactors (101A; 101B) are mounted in parallel, one being in service for extraction while the other is out of service for extraction and is then drained, cleaned and refilled, in order to conduct the extraction continuously. 10 - Apparatus according to one of claims 8 and 9, characterized in that part of the water from the supply water tank (108) forms the cooling circuit of the device before it is recycled into cooling ( 120) said feed water tank (108). 1/2 2/2 128