METHOD FOR REMOVING AN UNDESIRABLE SUBSTANCE FROM A BEVERAGE

Abstract

The invention relates to a method for removing an undesirable organic molecule, such as a pesticide, from a beverage, particularly wine, having a molecular weight between 220 and 420 g / mol and more than 16 atoms other than hydrogen. This method comprises contacting the beverage with a type Y zeolite having a Si / Al ratio greater than 7 and whose counter-cation is H+ or Na+. When applied to wine, this method does not adversely affect its organoleptic characteristics.

Description

Title of the invention: METHOD FOR REMOVING AN UNDESIRABLE SUBSTANCE FROM A BEVERAGE

[0001] The present invention falls within the field of beverage purification, in particular beverages obtained from plant matter, which may be contaminated by residues of plant protection products.

[0002] More particularly, the present invention relates to a method of removing an undesirable organic molecule contained in a beverage.

[0003] The invention is of particular, but not limited, interest in the field of the production of beverages obtained from viticultural products, in particular wines.

[0004] Plant protection products, commonly referred to as pesticides, which are used to treat vines, particularly to protect them against downy mildew, powdery mildew, etc., represent a significant source of exogenous contaminants in wine, a source about which the public is also the most informed. Indeed, recent press articles report widespread contamination of wines, whether produced using conventional winemaking processes or organic wines. It is specifically reported that, among the pesticide residues detected in wines, many molecules are possible or probable carcinogens, developmental or reproductive toxins, endocrine disruptors, or neurotoxins.Although no real toxicological risk has been associated with the presence in wines of residues from the phytosanitary treatment of vines, this presence is a major concern for consumers and producers.

[0005] Beyond the health aspect, new regulatory and commercial requirements have been emerging for several years, and the contamination of a wine by residues of plant protection products can harm its marketability.

[0006] To address this problem, studies are currently underway to limit the use of plant protection products for treating vines. These studies are exploring several avenues, including the development of new, less polluting vine treatment products, more disease-resistant grapevine varieties, biocontrol devices, and the responsible use of plant protection products. However, none of these studies has yet made it possible to completely replace the use of synthetic plant protection products for treating vines. Residues of these products may therefore still be present in the wines produced.

[0007] Few physical processes are currently available for satisfactorily removing pesticide residues from wines. Published experimental results indicate that among the agents tested, such as activated carbon, casein, gelatin, bentonite, and polyvinylpolypyrrolidone, treatment with activated carbon appears to be the most effective. However, treating wines with activated carbon can significantly affect other substances in the wine that are essential to its organoleptic properties, such as aromatic molecules and phenolic compounds.

[0008] Among the plant protection products, primarily insecticides or fungicides, commonly used for treating vines, the most frequent contain, as active ingredients, molecules with a complex structure and high molecular weight, exceeding 220 g / mol. Examples include iprodione, iprovalicarb, fenhexamide, fludioxonil, cyprodinil, boscalid, tebuconazole, fluopyram, fluopicolide, ametoctradine, spiroxamine, fenpyrazamine, fluxapyroxade, etc. Selectively removing such compounds from wines containing them, without affecting the organoleptic characteristics of these wines, proves particularly difficult. Therefore, there is currently a need for a process enabling such selective removal.

[0009] The present invention aims to propose such a process, more particularly a process which makes it possible to significantly reduce the concentration, in wines in particular and more generally in beverages, of the greatest possible number of organic phytosanitary molecules likely to be present therein, and in particular molecules of high molecular weight and high complexity, without negatively impacting the other physico-chemical characteristics, in particular the organoleptic characteristics, such as the color, smell and taste, of these beverages.

[0010] Additional objectives of the invention are that this process be easy to implement, and in particular that it be integrated, without requiring substantial modifications, into the methods commonly used for the manufacture of beverages, in particular, in the case of wines, into the usual winemaking methods.

[0011] The inventors have discovered that zeolites meeting specific characteristics make it possible to achieve these objectives, and in particular are capable of adsorbing in a specific and particularly efficient manner a large number of different phytosanitary molecules likely to be contained in wines, without degrading the organoleptic characteristics of the latter.

[0012] Thus, the present invention proposes a method for removing an undesirable organic molecule contained in a beverage, this molecule having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16. This process includes contacting this beverage with a type Y zeolite having a Si / Al ratio greater than 7 and whose counter-cation is H+ or Na+.

[0013] The process according to the invention makes it advantageous in particular to simultaneously eliminate from the beverage a plurality of undesirable organic molecules contained therein, each of these molecules having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16.

[0014] In the present description, by eliminating a molecule, we mean both a total elimination of the latter from the drink in which it is contained, and a partial elimination, that is to say a reduction of its concentration in the drink.

[0015] The invention aims in particular to achieve the highest possible elimination rate for each targeted undesirable organic molecule. Generally, this elimination rate is preferably greater than or equal to 60%. However, for certain specific molecules that are particularly difficult to eliminate, lower rates, such as around 40%, may be considered satisfactory.

[0016] In this description, the term "beverage" means any liquid food intended for human or animal consumption.

[0017] In particular embodiments of the invention, the beverage is obtained from, at least in part, ingredients of plant origin. However, this feature is not limiting to the invention, and the beverage may be formed in another way, for example, be water.

[0018] The beverage to which the process according to the invention is applied may be alcoholic or non-alcoholic. It may, for example, be fruit juice, beer, spirits, etc. In preferred embodiments of the invention, the beverage is wine, in particular red or white wine, or must, in particular grape must. The term "wine" here includes, in addition to wines themselves, special wines such as sparkling wines, as well as wine-based or wine-derived beverages, or more generally, beverages made from grapes.

[0019] Zeolites are microporous minerals, which can be natural or synthetic. More precisely, they are hydrated aluminosilicates, generally of alkali or alkaline earth metals, such as Ca2+, Mg2+, K+, or Na+, characterized by a three-dimensional anionic network of SiO4 and AlO4 tetrahedra linked to each other by sharing oxygen atoms.

[0020] Zeolites are known for their adsorption capacities. However, these capacities vary greatly depending on the type of zeolite and its characteristics. particulars, as well as the target to be adsorbed. Thus, in the field of oenology for example, while some zeolites have a good capacity for protein and tartaric stabilization of wine, and are currently proposed for this purpose, others have a much lower, or even zero, effectiveness.

[0021] Type Y zeolites, also called faujasites, are synthetic zeolites with a cubic crystallographic structure, corresponding to the general formula (I):

[0022] [Chem.l] (i)

[0023] where x, y and z represent integers and M represents an exchangeable cation, the Si / Al atomic ratio being greater than 1.5.

[0024] The zeolites implemented according to the invention are thus of the faujasite type, and they are more specifically defined by the following characteristics: - their Si / Al atomic ratio is greater than 7, and preferably less than 340, - their central counter-cation is H+ or Na+.

[0025] For each given zeolite, its type (faujasite, mordenite, etc.), its Si / Al ratio and the type of counter-cation that characterizes it, are commonly available from suppliers.

[0026] Alternatively, a person skilled in the art can determine them experimentally, by implementing classic characterization techniques in themselves.

[0027] Thus, a person skilled in the art can determine that a zeolite is of type Y, that is to say, is a faujasite, by X-ray diffractometry analysis, for example by means of a copper anticathode X-ray diffractometer (XCuk

[0028] The Si / AL ratio of a zeolite can be determined by elemental analysis by inductively coupled plasma optical emission spectrometry (ICP-OES), for example using an Agilent 5110 ICP-OES analyzer, after mineralization by microwave treatment, for example with the Anton-Paar Multiwave Pro mineralization system.

[0029] The central counter-cation of the zeolite can be identified by the same method, i.e. ICP-OES elemental analysis, after microwave mineralization. ​

[0030] The undesirable organic molecule target, which the process according to the invention aims to eliminate from the beverage, is defined by its molecular weight and by the number of atoms other than hydrogen contained in its structure. This number, which will be designated in this description by the abbreviation HAC (for the English " "Heavy Atom Count" (or the number of heavy atoms (here, heavy atoms are understood to be atoms other than hydrogen)) is particularly representative of the complexity of its structure.

[0031] The undesirable organic molecule is preferably a plant protection product, in particular an active molecule with pesticide properties, including in particular molecules with fungicidal activity and molecules with insecticidal activity, molecules with herbicidal or protective, regulatory or growth-stimulating properties for plants, or one of their derivatives. The undesirable organic molecule is in particular as defined in Article 3 of Directive 2009 / 128 / EC of the European Parliament and of the Council of 21 October 2009, in particular a plant protection product within the meaning of Regulation (EC) No 1107 / 2009 or a biocidal product as defined in Directive 98 / 8 / EC of the European Parliament and of the Council of 16 February 1998.

[0032] Thus, the undesirable organic molecule targeted by the process according to the invention is in particular a phytopharmaceutical molecule intended for one of the following uses: - to protect plants or plant products against all harmful organisms or to prevent the action of these; - to exert an action on the vital processes of plants, such as their growth; - ensure the preservation of plant products; - destroy unwanted plants or parts of plants; - to slow down or prevent undesirable plant growth.

[0033] Phytosanitary molecules commonly used for the treatment of vines are particularly targeted by the process according to the invention.

[0034] The phytosanitary molecule may in particular be chosen from among halogenated or polyhalogenated molecules, in particular organochlorine or organofluorine, such as fludioxonil, iprodione, fenbuconazole, valifenalate, tebuconazole, fluxapyroxade, mandipropamide, difenoconazole, pyraclostrobin, zoxamide, fenhexamide, tetraconazole, fluopicolide, fluopyram, boscalid, trifloxystrobin or quinoxyfen.

[0035] Alternatively, it may be a non-halogenated molecule, for example cyprodinil, benalaxyl, iprovalicarb, azoxystrobin, fenpyrazamine, tebufenozide, benthiavalicarb-isopropyl, kresoxime-Me, spiroxamine, amectoctradine, or even dimethomorph or metalaxyl, this list not being in any way limiting the invention.

[0036] All of these plant protection molecules have a molecular weight between 220 and 420 g / mol and an HAC greater than 16.

[0037] The process according to the invention advantageously makes it possible to efficiently eliminate such organic molecules from a beverage that contains them, including in one of any of their mixtures, using a low concentration of zeolite, specifically as low as 0.1 g per liter of beverage.

[0038] It is particularly simple and economical to implement.

[0039] In particular embodiments in which the beverage is a wine, it allows, without significantly disturbing the winemaking process, the effective removal of residues of plant protection products commonly used for the treatment of the vine, without adversely altering the organoleptic characteristics of the wine, thanks to the specific properties of the zeolite selected according to the invention, and in particular its high specific adsorption capacity of organic plant protection molecules with a molecular weight between 220 and 420 g / mol and an HAC greater than 16, which allows them to be removed from the liquid medium.Surprisingly, the zeolites according to the invention have little or no impact on the concentration in the beverage of lower molecular weight and less complex molecules associated with a lower number of atoms other than hydrogen, such as the molecules typically responsible for the organoleptic properties of wines. The mechanisms underlying this advantageous result will not be discussed here. However, it can be assumed that molecules with a molecular weight below 220 g / mol and a number of atoms other than hydrogen less than or equal to 16 remain less permanently present in the pores of the zeolites defined according to the invention, and are therefore less readily adsorbed by them. Advantageously, the use of the zeolites according to the invention also does not affect the concentration of phenolic compounds present in the wine.

[0040] The method according to the invention may also meet one or more of the characteristics described below, implemented in isolation or in each of their technically operative combinations.

[0041] As indicated above, the undesirable organic molecule targeted by the process according to the invention may contain one or more halogen atoms, such as chlorine and / or fluorine atoms. Preferably, it is free of bromine atoms, the zeolite selected according to the invention having a lower adsorption capacity for brominated molecules.

[0042] The undesirable organic molecule is also preferably, for a similar reason, devoid of a morpholine nucleus, i.e., of a motif:

[0043] [Chem.2]

[0044] Preferably, the undesirable organic molecule targeted by the process according to the invention has a topological polar surface area (TPSA) greater than 21 Å. The topological polar surface area of ​​a molecule is defined here, classically, as the sum of the surface area measured over all the polar atoms of the molecule, including their attached hydrogen atoms. It can be determined by any classical molecular modeling software, in particular by the Cactvs 3.4.8.18 software (PubChem Release 2021.05.07). The inventors have observed that the adsorption capacity of the zeolite selected according to the invention is lower with respect to molecules with a topological polar surface area less than 21 Å.

[0045] The undesirable organic molecule also preferably has a logP, i.e. an octanol / water partition coefficient, denoting the hydrophobicity of the molecule, which is greater than or equal to 1.7, and preferably less than or equal to 5.1. Here again, the adsorption capacity of the zeolite selected according to the invention is somewhat lower with respect to molecules with a logP less than 1.6. The logP of a molecule can be measured by any conventional algorithmic calculation software, in particular by the atom addition calculation program XLogP3-AA, version 3.0 for example.

[0046] Preferably, the undesirable organic molecule targeted by the process according to the invention has a number of rotatable bonds greater than 0. The number of rotatable bonds in a molecule is defined here, classically, as the number of bonds that are free to rotate about themselves, more precisely the number of single bonds, not contained in a ring, linked to a non-terminal heavy atom (i.e., other than hydrogen), and other than CN bonds. The number of rotatable bonds in a given molecule can notably be determined by any classical molecular modeling software, in particular by the Cactvs 3.4.8.18 software (PubChem Press Release 2021.05.07).Organic molecules with a number of rotating bonds greater than 0 exhibit, in particular, a certain degree of flexibility, which advantageously increases their level of adsorption by the particular zeolites defined according to the invention.

[0047] The type Y zeolite implemented according to the invention preferably has a Si / Al ratio greater than or equal to 40, in particular between 40 and 340. In such a range, it exhibits a particularly high adsorption capacity of the target organic molecules of the process according to the invention.

[0048] Preferably, the zeolite has not undergone any pretreatment prior to its contact with the beverage, in particular no activation pretreatment, for example by heating with electromagnetic waves.

[0049] It is in powder form, the particle size, as measured by laser diffraction particle size analysis, for example using a Mastersizer 2000 device from Malvern Instruments, in diameter mode, being preferably defined by a d(0.5), i.e. diameter below which 50% of the particles are between 4 and 6 pm.

[0050] In particular embodiments of the invention, the contact time of the beverage with the zeolite is between 1 minute and 36 hours, in particular between 1 minute and 30 hours, in particular between 1 minute and 24 hours, and for example between 1 minute and 12 hours. In other particular embodiments of the invention, it is between 1 minute and 2 hours, in particular between 30 and 90 minutes. It may, for example, be approximately 1 hour, or even approximately 24 hours, depending on when this step is carried out within a more overall winemaking process.

[0051] This contacting step can be carried out dynamically or statically.

[0052] Thus, in particular embodiments of the invention, the contact of the zeolite with the drink is achieved by circulating the drink in a reactor containing the zeolite.

[0053] This reactor is preferably continuously supplied with the beverage to be treated.

[0054] In particular embodiments of the invention, the reactor includes at the outlet a filtration membrane, with a cut-off threshold preferably between 0.20 and 0.45 pm, retaining the particles inside the reactor and allowing the passage of the treated beverage.

[0055] The flow rate of the beverage in the reactor is then advantageously adjusted to obtain the desired contact time between the beverage and the zeolite, allowing the adsorption by the latter of the undesirable target organic molecule(s), and thereby their elimination from the beverage circulating in the reactor.

[0056] In alternative embodiments of the invention, the zeolite is brought into contact with the beverage by introducing the zeolite into the beverage, for example in powder form, or as a suspension in a liquid vehicle, such as water, and keeping these products in contact with each other, under agitation or No, for the required duration. The concentration of zeolite introduced into the drink is preferably between 0.01 and 1 g / l, preferably still between 0.05 and 1 g / l, preferably between 0.1 and 1 g / l, for example between 0.1 and 0.5 g / l.

[0057] The process according to the invention then preferably includes, after the step of bringing the beverage into contact with the zeolite, a step of separating the beverage and the zeolite, including the charged zeolite, that is to say, in the cavities of which are lodged the undesirable organic molecule(s) which have been adsorbed.

[0058] Any conventional separation technique, particularly one commonly used in wineries, can be employed within the scope of the invention. The separation of the beverage and the zeolite can notably be achieved by filtration, using any conventional filtration device with a porosity capable of retaining the zeolites, particularly with a cutoff point of 0.20 to 0.45 µm.

[0059] Examples of such filtration devices include plate filters, press filters, rotary filters under reduced pressure, lenticular module filters, cartridge filters, continuous alluvial filters, tangential filters with organic or mineral membranes, or depth filtration plates, such as are classically used in the field of oenology.

[0060] Filtration can be carried out in batches, or continuously.

[0061] In general, the process according to the invention aims to fit into the broader context of a beverage production process, preferably by modifying the usual steps of this production process as little as possible.

[0062] The process according to the invention can be implemented at any time during such a manufacturing process.

[0063] In particular, it can be implemented at the end of a process for producing the classic beverage itself, before the bottling of said beverage, the final step of this production process.

[0064] It can, for example, be implemented immediately before the bottling step, or before a final filtration step of the beverage prior to the bottling step, if such a filtration step exists. Advantageously, this beverage filtration step, implemented in a conventional manner in the beverage production process, also separates the zeolite, in particular the zeolite containing the undesirable molecule(s), from the beverage, thus completing the final step of the removal process according to the invention.

[0065] In configurations where the beverage is wine, the process according to the invention can be carried out, for the step of contacting the wine with the zeolite, after the alcoholic and, if applicable, malolactic fermentation steps of the winemaking process, and, if it exists, at the end of or after the wine aging step, before bottling. The filtration step of the process according to the invention can then coincide with, where it exists, the classic final filtration stage of the winemaking process.

[0066] More generally, in particular embodiments of the invention, the step of bringing the drink into contact with the zeolite is carried out before a final filtration step, which is classic in itself, of a process for preparing the drink.

[0067] Another object of the invention is the use of a type Y zeolite having a Si / Al ratio greater than 7 and whose counter-cation is H+ or Na+, to eliminate from a beverage one, or a plurality of, undesirable organic molecule(s) having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16, which are contained therein.

[0068] This use includes bringing the beverage into contact with the zeolite. It may meet one or more of the characteristics described above with reference to the process according to the invention, concerning both the steps of this process, the zeolite used and the undesirable organic molecule(s) targeted.

[0069] In particular, the undesirable organic molecule may be a plant protection product. It is notably selected from among the following substances: ametoctradine, boscalid, fenhexamide, fenpyrazamine, fludioxonil, fluopicolide, fluopyram, fluxapyroxad, iprovalicarb, benalaxyl, benthiavalicarb-isopropyl, cyflufenamide, cyprodinil, difenoconazole, fenbuconazole, iprodione, kresoxim-Me, mandipropamide, spiroxamine, tebuconazole, tetraconazole, trifloxystrobin, valifenalate, zoxamide. These substances may be present in the beverage alone or in any mixture thereof.

[0070] It can otherwise be the dimethomorph or the metalaxyl.

[0071] The present invention also relates to a process for preparing a beverage, comprising a final step of bottling this beverage, as well as, prior to this final bottling step, preferably at the end of the process, the implementation of an elimination process according to the invention, as described above, for removing from said beverage one, or a plurality of, undesirable organic molecule(s) having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16, which are contained therein.

[0072] The step of bringing the beverage into contact with the zeolite in this elimination process is preferably carried out before a final filtration step in the overall beverage production process.

[0073] The invention thus relates in particular to a method for producing wine, which includes applying to this wine, before a step of bottling the conventional wine itself, preferably immediately before this bottling step. bottle, or before a final filtration step preceding this bottling step, also conventional in itself, of a process to remove an undesirable organic molecule from a beverage according to the invention.

[0074] The features and advantages of the invention will become more apparent in the light of the following implementation examples, provided by way of illustration only and in no way limiting the invention, with the support of Figures 1 to 6, in which:

[0075] [Fig-1] Figure [Fig.1] represents a bar graph showing the elimination rate a means of 10 phytosanitary molecules contained in a red wine, by treatment with faujasites with counter-cation H+ or Na+, and of different Si / Al ratios, the faujasites Fl to F5 being in accordance with the invention, and the faujasites F7 to F10 not in accordance with the invention.

[0076] [Fig.2] Figure [Fig.2] represents a bar graph showing the result of a test triangular sensory analysis (jury of 40 people), expressed in terms of the number of correct answers, concerning the distinction, for each of 3 different red wines (Red Wine 1, Red Wine 2, Red Wine 3), between the untreated wine and the wine treated with a zeolite according to the invention, at a rate of 0.1 g / l for 1 h; the horizontal line between the ordinate values ​​18 and 20 indicates the limit of significance.

[0077] [Fig.3] Figure [Fig.3] shows a bar graph representing the Polyphenol Index Totals, determined by measurement of absorbance at 280 nm, respectively for a red wine: untreated (“Control Wine”), untreated and filtered (“Filtered Control Wine”), or treated with a zeolite according to the invention, at 0.1 g / l for 1 h, then filtered (“Treated Wine”).

[0078] [Fig.4] Fig.4 shows a bar graph representing the sum of concentrations of different aromatic compounds in a red wine: untreated (“Untreated control”) or treated with a zeolite according to the invention, at 0.1 g / l for 1 h, then filtered (“Treated wine”).

[0079] [Fig. 5] Figure 5 shows a bar graph representing the parameters chromatics in the CIELAB space determined for a red wine: untreated and filtered (“Filtered Wine”) or treated with a zeolite according to the invention, at 0.1 g / l for 1 h, then filtered (“Filtered Treated Wine”).

[0080] [Fig.6] Figure [Fig.6] shows a bar graph representing the characteristics physicochemical properties determined by Fourier transform infrared analysis (Volume alcohol content "TAV", glucose and fructose sugar concentration "Sugars G / F" (g / 1), total acidity "AT" (g / 1), pH, volatile acidity "AV" (g / 1)) for a red wine: untreated and filtered ("Filtered Wine") or treated with a zeolite according to the invention, at 0.1 g / 1 for 1 h, then filtered ("Filtered Treated Wine").

[0081] Example 1 - Zeolites

[0082] The zeolites described in Table 1 were tested in the examples below. Zeolites Fl to F5 conform to the invention. The other zeolites do not conform to the invention.

[0083] The characteristics of each zeolite were determined as follows: - structure, by X-ray diffractometry analysis, using a copper anticathode X-ray diffractometer (XCuk

[0084] [Tables 1] Zeolite Structure Si / Al Ratio Cation Fl Faujasite Y 7.8 H+ F2 Faujasite Y 332.2 H+ F3 Faujasite Y 54 H+ F4 Faujasite Y 40.5 Na+ F5 Faujasite Y 39.2 H+ F7 Faujasite Y 3.2 Na+ F8 Faujasite Y 3.8 H+ F9 Faujasite Y 3.4 H+ F10 Faujasite Y 6.3 H+ Fil Faujasite Y 15.9 nH4+ Ml Mordenite 9.3 nH4+ M2 Mordenite 9.6 Na+ M3 Mordenite 110.1 H+ L1 Type-L 3.3 H+

[0085] Table 1 - Characteristics of the tested zeolites ​

[0086] Example 2 - Elimination of a plurality of phytosanitary molecules contained in a wine

[0087] This experiment is carried out on a Bordeaux red wine (blend of Merlot, Cabernet Sauvignon and Cabernet Franc) comprising the concentrations of different phytosanitary molecules indicated in Table 2, all having a molecular weight between 220 and 420 g / mol and an HAC greater than 16.

[0088] [Tables2] Molecule Abbreviation Molecular Weight (g / mol) HAC Concentration (pg / L) Ametoctradine Ame 275.39 20 2.04 Boscalid Bos 343.2 23 31.26 Dimethomorph Dim 387.9 27 7.08 Fenhexamide Feh 302.2 19 32.73 Fenpyrazamine Fep 331.4 23 3.86 Fludioxonil Fld 248.18 18 1.51 Fluopicolide Fpi 383.6 23 21.07 Fluopyram Fpy 396.71 26 9.89 Fluxapyroxad Flx 381.3 27 3.44 Iprovalicarbe Ipr 320.4 23 4.97

[0089] Table 2 - Initial concentrations of plant protection molecules in wine

[0090] The following zeolites are tested: - zeolites conforming to the invention: Fl, F2, F3, F4, F5; - zeolites not conforming to the invention: F7, F8, F9, F10, Fil, Ml, M2, M3, Ll.

[0091] For each zeolite, a sample of wine is treated for 1 h, under agitation, with 0.1 g / l of zeolite.

[0092] More specifically, 200 mL Erlenmeyer flasks are filled with wine (100 mL), and a magnetic stir bar is added. The flasks are placed on a shaking plate at 20°C. Powdered zeolites are added (0.01 g per flask). After 1 h of contact, the contents of each flask are filtered through a polyvinylidene fluoride (PVDF) membrane to retain the zeolite. The recovered liquid is stored in a cool place before analysis.

[0093] Before and after this step, the initial and final concentrations of each molecule in the sample are measured by High-Performance Liquid Chromatography coupled with Mass Spectrometry detection (HPLC-MS), developed according to the QuEChERS method collection. Quantification is performed using internal calibration. For analysis and quantification, the high-performance liquid chromatograph (1200 series) is coupled to a 6430 triple quadrupole mass spectrometer (Agilent Technologies). The column is a C18 type with dimensions of 2.1 x 150 mm and a porosity of 2.7 pm. The sample is injected at a rate of 10 pL onto the column, which is thermostated at 40°C. The solvent gradient starts at 95% water and ends at 100% acetonitrile with a flow rate of 0.3 mL / min*. The mass spectrometer is equipped of an electro-spray ionization source operating in negative and positive mode. Nitrogen is used for desolvation and in the collision cell.

[0094] The elimination rate of each molecule is calculated using the following equation:

[0095] [Math.l] Gî - Cf

[0096] where Ci represents the initial concentration of the molecule in the sample, and Cf its final concentration.

[0097] The results obtained are shown in Table 3, for each zeolite and for each molecule. Also shown in this table, for each zeolite tested, is the average elimination rate (“Moy”) obtained for all the molecules.

[0098] [Tables3] Zeolithe Ame (%) Bos (%) Dim (%) Feh (%) Fep (%) Fld (%) Fpi (%) Fpy (%) Flx (%) Ipr (%) Moy (%) Fl 97.5 75.6 19.0 62.2 66.9 68.1 96.9 96.3 75.9 53.1 76.9 F2 98.8 86.4 23.6 72.3 77.2 80.3 98.0 97.9 83.3 64.9 84.4 F3 99.5 88.3 18.9 80.0 82.1 82.8 98.6 98.9 85.1 67.6 87.0 F4 98.6 79.3 16.9 68.7 82.2 74.9 99.0 98.1 80.8 54.6 81.8 F5 99.2 57.3 15.6 55.5 81.9 60.6 98.2 97.3 63.4 40.2 72.6 F7 27.3 10.2 2.0 8.0 13.5 5.0 15.1 7.0 14.4 0.5 11.2 F8 96.0 6.6 1.0 6.7 23.4 15.4 69.2 63.5 15.2 5.8 33.5 F9 66.2 12.1 0 0 8.4 7.2 9.0 1.9 7.7 0 11,7 F10 97,1 13.2 15.2 20.4 28.5 22.0 68.7 64.6 15.9 9.9 37.8 Fil 98.0 17.2 3.9 21.1 45.7 32.5 81.7 73.8 22.0 13.5 45.1 Ml 0 0 0 0 6.8 5.1 1.6 0.4 9.3 0.3 2.3 M2 19.5 0.1 7.3 3.5 16.8 5.1 13.4 12.9 10.1 9.3 10.1 M3 12.6 0 5.8 7.7 13.2 12.1 16.5 9.9 14.6 11.9 10.6 L1 25.1 11.9 12.1 20.6 15.6 2.5 20.8 15.9 17.3 15.6 16.1

[0099] Table 3 - Removal rate (in %) of molecules by the different zeolites - Mean represents the average removal rate obtained by the zeolite for all molecules

[0100] As can be seen, the zeolites according to the invention Fl to F5 exhibit particularly high average removal rates for all molecules, exceeding 70%. This removal efficiency is observed for all molecules tested, with the exception of dimethomorph, for which the removal rates are lower, but still higher than those obtained for the other zeolites. Overall, the zeolites according to the invention prove to be by far the most effective among all those tested.

[0101] Comparative faujasites F7 to Fl 1 are more effective than mordenites and F-type zeolite, but much less so than the faujasites according to the invention, including with regard to faujasite F10, whose Si / Al ratio is close to 7, and faujasite Fl 1, with a Si / Al ratio much greater than 7 but whose counter-cation is the ammonium ion.

[0102] Figure 1 shows the average elimination rate obtained for all the tested molecules for each of the faujasites whose counter-cation is H+ or Na+, these faujasites being ranked by increasing Si / Al ratio. A significant increase in the average elimination rate is clearly observed as soon as the Si / Al ratio of the faujasite becomes greater than 7. Above 40, this rate is greater than 80% and varies less significantly.

[0103] Example 3 - Tests in several wines

[0104] This experiment is carried out with the zeolite according to the invention F4, in different wines of various origins, some of which are taken at the end of aging, others after bottling, and of various vintages, from 2014 to 2020: 8 red wines (VI to V7) and 1 white wine (V8).

[0105] Each of these wines contains a mixture of different plant protection molecules. In addition to the molecules described in Table 2, the molecules described in Table 4 are present in some of these mixtures.

[0106] [Tables4] Molecule Molecular Weight (g / mol) HAC Benalaxyl 325.4 24 Benthivalicarb-isopropyl 381.5 26 Cyflufenamide 412.4 29 Cyprodinil 225.29 17 Difenoconazole 406.3 27 Fenbuconazole 336.8 24 Iprodione 330.16 21 Kresoxim-Me 313.3 23 Mandipropamide 411.9 29 Metalaxyl 279.33 20 Spiroxamine 297.5 21 Tebuconazole 307.8 21 Tetraconazole 372.14 23 Trifloxystrobin 408.4 29 Valifenalate 398.9 27 Zoxamide 336.6 20 Pyrimethanil 199.25 15

[0107] Table 4 - Phytosanitary molecules contained in wines

[0108] Among these molecules, having a molecular weight and HAC as targeted by the invention, unlike the other molecules, metalaxyl has a logP less than 1.7 (equal to 1.6).

[0109] Pyrimethanil does not meet the criteria of the target according to the invention.

[0110] The initial composition of the wine samples in each of the molecules phytosanitary, measured by HPLC-MS as described in Example 2, is shown in Table 5. [YES] [Tables 5] VI (Pg / l) V2 (Pg / l) V3 (pg / 1) V4 (Pg / l) V5 (pg / 1) V6 (pg / 1) V7 (Pg / l) V8 (pg / 1) Ametoctradine 9 1.9 3.4 5.6 1.4 - 3.5 3.6 Benalaxyl - - 0.43 - - - - 0.1 Benthiavalicarb-iPr - 3.1 - - - - - - Boscalid 59 3.6 4.2 261 1.3 48.8 11.8 0.3 Cyflufenamide - - 0.1 - 2.5 - - - Cyprodinil - 3 2.2 11 - - - 1.3 Difenoconazole - - 0.13 - - - - - Fenbuconazole - - 0.30 - - - - - Fenhexamide - 25 13.1 149 16.1 30.7 59.1 32.1 Fenpyraz amine - - 9.5 - 2.0 - 15.1 16.3 Fludioxonil - 3.7 3.0 9.5 2.2 - - 2.6 Fluopicolide 6 0.7 4.0 76.4 4.9 26.6 23.2 1.9 Fluopyram - 1.9 1.0 19.1 - 5.8 25.7 0.2 Fluxapyroxad - - - - - - 16.0 - Iprodione - 29 - - - - - - Iprovalicarb - 1.5 0.17 - - - 14.0 2.0 Kresoxim-Me - - 0.09 - - - - - Mandipropamide - 4.4 0.3 - - - - - Metalaxyl - - 0.70 - 1.9 - - 0.3 Spiroxamine - - 1.2 1 - - - 0.3 Tebuconazole - 2.3 1.3 6.5 1.8 - - 0.3 Pyrimethanil 106 5.0 12.3 146 8.3 25.4 110.8 6.7

[0112] Table 5 - Initial concentrations of molecules in wines

[0113] Each wine sample is treated with F4 zeolite at a rate of 0.1 g / l for 1 h, as described in example 2.

[0114] After filtration, the final composition of the wine samples in each of the phytosanitary molecules is measured by HPLC-MS as described in Example 2.

[0115] For each wine sample and each molecule, the removal rate is calculated as indicated in Example 2.

[0116] The results obtained, in terms of % elimination of molecules, are shown in Table 6.

[0117] [Tableauxô] VI (%) V2 (%) V3 (%) V4 (%) V5 (%) V6 (%) V7 (%) V8 (%) Moy (%) Ametoctradine 100 100 100 100 100 - 100 100 100 Benalaxyl - - 97 - - - - 100 98 Benthiavalicarb-iPr - 77 - - - - - - 77 Boscalide 73 83 79 73 71 77 84 100 80 Cyflufénamide - - 100 - 81 - - - 90 Cyprodinil - 87 85 89 - - - 71 83 Difénoconazole - - 100 - - - - - 100 Fenbuconazole - - 100 - - - - - 100 Fenhexamide - 72 79 66 63 69 66 83 71 Fenpyraz amine - - 86 - 79 - 78 82 81 Fludioxonil - 84 87 78 80 - - 84 81 Fluopicolide 95 100 99 99 100 99 98 100 99 Fluopyrame - 97 100 98 - 99 98 100 99 Fluxapyroxad - - - - - - 78 - 79 Iprodione - 62 - - - - - - 62 Iprovalicarbe - 67 74 - - - 62 69 67 Kresoxim-Me - - 89 - - - - - 89 Mandipropamide - 95 100 - - - - 100 98 Métalaxyl - - 49 - 30 - - 41 40 Spiroxamine - - 100 100 - - - 100 100 Tébuconazole - 100 95 100 98 - - 100 99 Pyriméthanil 39 40 37 27 18 27 9 23 27

[0118] Table 6 - Removal rate (in %) of molecules by zeolite - Avg represents the average removal rate obtained for each molecule

[0119] For the vast majority of target molecules, which have very different structures, a very good average elimination rate is observed, exceeding 60%, and exceeding 80% for 16 of them. This average elimination rate is even between 98% and 100% for many of the molecules. This result is obtained regardless of the wine tested, whether red (VI to V7) or white (V8). For the metalaxyl target, the elimination rate is lower, but still satisfactory.

[0120] Pyrimethanil, which has a lower molecular weight and HAC than the molecules targeted by the invention, is very poorly eliminated.

[0121] These results demonstrate the strong adsorption capacity of the zeolite according to the invention with respect to the target molecules as defined by the invention, whereas the adsorption capacity by this zeolite of a molecule outside the criteria for defining this target is much less important.

[0122] Example 4 - Impact on the organoleptic properties of wines

[0123] The possible impact of the process according to the invention on the treated wine was evaluated by analysis of the classic physicochemical parameters of the wines, analysis of the chromatic characteristics of the wines in the CIELAB space, determination of the Total Polyphenol Index (TPI) and the concentration of aromatic molecules (different esters and 2-phenyl ethanol), and sensory analysis.

[0124] Three red wines (Red Wine 1, Red Wine 2, and Red Wine 3), from different grape varieties and vintages, were treated with zeolite F4 according to the invention. For each wine, 5 liters were treated with the zeolite (contact time 1 hour, concentration 0.1 g / L), as described in Example 2, and then filtered to remove the zeolite. For each wine, a control sample underwent the same process, but without the zeolite. Following these operations, the wines were bottled, sealed with screw caps, and stored for 3 months.

[0125] At the end of this aging period, the wines were analyzed and submitted to a tasting panel in the context of triangular tests, as mentioned in section 4.1. The analyses described in sections 4.2, 4.3, 4.4 below were also carried out on the wines obtained during these tests.

[0126] 4.1 / Sensory analyses

[0127] Sensory analyses were carried out in a standardized tasting room. The isolated workstations ensured the smooth running of the tasting and prevented the panel from conferring.

[0128] The tastings were carried out in standardized glasses (AFNOR-NFV 09-110 standard) that were transparent for the wine tests and in black glasses for the perception threshold tests with water. Each glass was coded with a randomly assigned three-digit number.

[0129] A triangular test was performed according to the procedure described in standard NF EN ISO 4120, allowing the determination of whether there is a perceptible sensory difference or a similarity between samples of two products. The method is a forced-choice procedure.

[0130] The glasses were filled out of sight of the subjects and in an identical manner, i.e. according to the same methodology, the same quantity, at the same temperature.

[0131] For this experiment, the jury was composed of 40 tasters. The profile of the jury was random, ranging from the novice, inexperienced in wine and its tasting, to the expert, perfectly familiar with the profile of a wine and able to recognize its descriptors and its defects.

[0132] Protocol sheets and response forms were prepared so that each of the tasters would have a tasting path different from the others, in order to avoid olfactory fatigue bias.

[0133] For each wine, each taster was specifically asked to distinguish between the wine treated with zeolite according to the invention and the untreated wine. The results obtained, in terms of the number of correct answers, are shown in [Fig. 2]. It can be observed that for each wine, the tasting panel was unable to distinguish the wine treated with zeolite from the untreated control wine (number of correct answers below the significance level).

[0134] 4.2 / Total Polyphenol Index

[0135] In order to estimate the overall polyphenol content, measurements in the ultraviolet (UV) spectrum at 280 nm and under a 10 mm optical path length, of the characteristic absorbance of delocalized electrons from the benzene rings of the polyphenols, were carried out on Red Wine 1 (treated with zeolite F4 and filtered), using a Jasco V-630 spectrophotometer. The wine was previously diluted by a factor of 100 (OIV, Codex Oenologique Internationale, 2012). The total polyphenol index (TPI) at 280 nm was calculated using the following formula:

[0136] [Math.2] IPT ~ d280 x dilution

[0137] in which "d280" represents the absorbance measured at 280 nm and "dilution" represents the dilution factor of the wine (100 in this experiment).

[0138] For comparison, the same measurement was carried out for untreated, unfiltered wine and for untreated, filtered wine. Three repetitions were carried out for each wine analyzed.

[0139] The results obtained for Red Wine 1 are shown as an example in [Fig.3]. No significant difference is observed between the modalities tested.

[0140] 4.3 / Ester dosage

[0141] The method implemented, allowing the quantification of nonpolar esters contained in wine, by headspace solid phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS), is as described in the publication by Antalick et al., 2010, Food Chemistry, 121: 1236-1245.

[0142] For this assay, four internal standards in alcoholic solution were used: ethyl-d5 butyrate (187 mg / L), ethyl-d5 hexanoate (271 mg / L), ethyl-d5 octanoate (262 mg / L), and ethyl-d5 cinnamate (174 mg / L). 20 pL of the internal standard solution was added to 25 mL of wine.

[0143] The mixture was homogenized, and then a 10 mL aliquot was placed in an SPME bottle previously filled with 3.5 g of NaCl. The bottle was sealed with a metal cap covered with a silicone septum and then shaken for a few seconds to homogenize its contents.

[0144] The concentrations of nonpolar esters (ethyl propanoate, ethyl isobutyrate, isobutyl acetate, ethyl butyrate, ethyl 2-methylbutyrate, ethyl isovalerate, isoamyl acetate, ethyl hexanoate, methyl salicylate, phenylethanol acetate) and 2-phenyl ethanol were measured by HS-SPME-GC-MS on RI red wine (treated with F4 zeolite), using an HP 5890 instrument according to the following parameters: - BP21 column, 50 m x 0.32 mm, film thickness 0.25 µm; - injector: polydimethylsiloxane, film thickness 100 pm, adsorption temperature 40 °C for 30 min; stirring speed 500 rpm; desorption parameters: injector temperature 250 °C, duration 15 min, splitless mode (45 s); - carrier gas: helium N55, flow rate 2 mL / min; - temperature programming: 40 °C maintained for 5 min, 5 °C / min up to 220 °C maintained for 30 min; - detector: mass spectrometer operating in electron impact HP 5972, ionization energy 70 eV, temperature 280 °C, detection in SIM mode.

[0145] For comparison, the same measurement was carried out for the untreated, filtered wine. Three repetitions were performed for each wine analyzed.

[0146] The results obtained for Red Wine 1, expressed as the sum of the concentrations of measured aromatic compounds, are shown as an example in [Fig. 4]. It can be observed that the removal of aromatic compounds is negligible compared to the control (loss of 0.1%). This impact is not significant.

[0147] 4.4 / Determination of colorimetric parameters

[0148] Measurements of the chromatic parameters of the wines in the CIELAB color space were carried out on Red Wine 1 (treated with F4 zeolite and filtered) according to the protocol described in OIV-MA-AS2-11: R2006. The spectrophotometer used was a Jasco V-630. For comparison, the same measurement was carried out for the untreated, filtered wine.

[0149] The results obtained are shown in [Fig. 5]. No difference is detected between the untreated wine filtered and the treated wine filtered according to the invention. The AE parameter, which characterizes the overall colorimetric difference between the two wines, is 0.25, well below the threshold value for detection by the naked eye, equal to 3 (Garcla-Marino et al., 2010, Analytica Chimica Acta, 660(1): 134-142).

[0150] 4.5 / Classical chemical parameters of wines

[0151] For each wine treated with F4 zeolite and filtered as described above, the following classic physicochemical characteristics were measured using a WineScan® 79000 (Foss) Fourier transform infrared wine analyzer: - Alcohol by volume (ABV), - concentration of sugars (glucose and fructose), - total acidity (TA), -pH, - volatile acidity (AV).

[0152] For comparison, the same measurement was carried out for untreated filtered wine.

[0153] The results obtained for Red Wine 1 are shown as an example on the [Fig.6].

[0154] Again, no significant difference is observed between the wine treated according to the invention and the untreated wine.

Claims

Demands

1. A method for removing an undesirable organic molecule from a beverage, said molecule having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16, said undesirable organic molecule being a plant protection product selected from fludioxonil, iprodione, fenbuconazole, valifenalate, tebuconazole, fluxapyroxade, mandipropamide, difenoconazole, pyraclostrobin, zoxamide, fenhexamide, tetraconazole, fluopicolide, fluopyram, boscalide, trifloxystrobin, quinoxyfen, cyprodinil, benalaxyl, iprovalicarb, azoxystrobin, fenpyrazamine, tebufenozide, benthiavalicarb-isopropyl, the kresoxime-Me, spiroxamine, amectoctradine, dimethomorph and metalaxyl, characterized in that said beverage is a wine, must or beer,and in that it includes bringing said beverage into contact with a type Y zeolite having a Si / Al atomic ratio greater than 7 and whose counter-cation is H+ or Na+.

2. A method according to claim 1, wherein the Si / Al ratio of said zeolite is greater than or equal to 40.

3. A method according to claim 1 or 2, wherein the duration of contact of said beverage with said zeolite is between 1 minute and 36 hours.

4. A method according to any one of claims 1 to 3, wherein the contact of said zeolite with said beverage is effected by introducing said zeolite into said beverage.

5. A method according to claim 4, wherein the contacting of said zeolite with said beverage is carried out by introducing said zeolite into said beverage in a concentration of between 0.01 and 1 g / l.

6. A method according to claim 5, wherein the contacting of said zeolite with said beverage is carried out by introducing said zeolite into said beverage in a concentration of between 0.1 and 0.5 g / l.

7. A method according to any one of claims 1 to 3, wherein the contacting of said zeolite with said beverage is carried out by circulating said beverage through a reactor containing said zeolite.

8. A method according to any one of claims 1 to 7, comprising, after the step of bringing said beverage into contact with said zeolite, a step of separating said zeolite and said beverage.

9. Use of a type Y zeolite having a Si / Al ratio greater than 7 and having H+ or Na+ as its counter-cation, for removing from wine, must or beer, an undesirable organic molecule having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16, said undesirable organic molecule being a plant protection product selected from fludioxonil, iprodione, fenbuconazole, valifenalate, tebuconazole, fluxapyroxade, mandipropamide, difenoconazole, pyraclostrobin, zoxamide, fenhexamide, tetraconazole, fluopicolide, fluopyram, boscalide, trifloxystrobin, quinoxyfen, cyprodinil, benalaxyl, iprovalicarb, azoxystrobin, fenpyrazamine, tebufenozide, benthiavalicarb-isopropyl, kresoxime-Me, spiroxamine, amectoctradine, dimethomorph and metalaxyl.

10. A process for producing a beverage, comprising a final step of bottling said beverage, said beverage being a wine, a must or a beer, characterized in that it comprises, prior to this final bottling step, the implementation of a process according to any one of claims 1 to 8 for removing from said beverage an undesirable organic molecule having a molecular weight between 220 and 420 g / mol and a number of atoms other than hydrogen greater than 16.

11. A process for preparing a beverage according to claim 10, comprising a final filtration step of said beverage, and wherein the step of contacting said beverage with said zeolite of said process according to any one of claims 1 to 8, is carried out before said final filtration step.

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