Three-dimensional porous structure based on glass fibers comprising a coating comprising particles of MOFs and / or zeolites

Abstract

Porous three-dimensional structure based on glass fibers, coated at least partially with a coating comprising particles bound by a binder, preferably consisting of particles bound by a binder, said particles being essentially particles of a material chosen from MOFs, zeolites and their mixtures, said binder comprising a crosslinked polymer chosen from a crosslinked polyacrylate, a crosslinked epoxide, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and their mixtures.

Description

Title of the invention: Three-dimensional porous structure based on glass fibers comprising a coating comprising particles of MOFs and / or zeolites Technical field

[0001] The present invention relates to a three-dimensional structure comprising a coating comprising particles of MOFs and / or zeolites. Prior art

[0002] As is well known, a metal-organic network, or "Metal Organic Framework", most often called "MOF" according to the English abbreviation, is a material consisting of metal ions or metal clusters and organic ligands, organized so as to form a porous crystalline network, and a zeolite is a crystallized aluminosilicate having a nanoporous system consisting of a network of interconnected or non-interconnected channels and cages occupied by cations.

[0003] Their high microporosity and specific surface area make it possible to envisage numerous industrial applications, particularly in the fields of gas storage or separation, as well as in catalysis.

[0004] Porous three-dimensional structures comprising particles of MOFs or zeolites on a metal support are known, and are notably used to adsorb molecules or carry out separation, notably of gases.

[0005] There is a need for three-dimensional structures supporting such higher performance particles.

[0006] One aim of the invention is to meet, at least partially, this need. Description of the invention

[0007] According to the invention, this aim is achieved by means of a porous three-dimensional structure based on glass fibers, coated, at least partially, with a coating comprising particles bound by a binder, preferably consisting of particles bound by a binder, said particles being essentially particles of an adsorbent material chosen from MOFs, zeolites and mixtures thereof, said binder comprising a crosslinked polymer chosen from a crosslinked polyacrylate, a crosslinked epoxide, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and mixtures thereof. An adsorbent material is in particular useful for adsorbing molecules in particular present in a fluid such as a gas or a liquid, for example toluene, CO2, VOCs.

[0008] The inventors discovered that the three-dimensional structure according to the invention presented, for an equivalent accessible surface, a greater quantity of material adsorbent, which makes it possible to improve the performance of said three-dimensional porous structure.

[0009] Preferably, the porous three-dimensional structure coated according to the invention also has one or more of the following optional characteristics: - The porous three-dimensional structure based on glass fibers is a monolith comprising at least one channel, preferably several channels separated by walls. - The average wall thickness between the channels is greater than or equal to 0.1 mm and less than or equal to 1 mm. - The number of channels per unit area, in a cross-section of said three-dimensional structure is greater than 3 / cm 2 and less than 80 / cm2. - The porous three-dimensional structure based on glass fibers contains more than 35% glass fibers, in mass percentage. - The porous three-dimensional structure based on glass fibers has corrugation on at least part of its surface. - The MOF is chosen from MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-199, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-63, MIL-100, MIL101, ZIF-57, SUM-102, SUM-103 and mixtures thereof, and the zeolite is chosen from zeolites of the FAU, MFI, LT A, MOR, BEA, FER families, and mixtures thereof. - The particles are MOF particles. - The particles are zeolite particles. - The binder comprises a crosslinked polyacrylate, preferably consists essentially of a crosslinked polyacrylate, and more preferably, consists of a crosslinked polyacrylate. - The ratio of the quantity of binder, to the sum of the mass of the MOF and zeolite particles and the mass of binder, is greater than or equal to 1% and less than or equal to 30%. - The ratio of the quantity of binder, to the sum of the mass of the MOF and zeolite particles and the mass of binder, is greater than or equal to 5%. - More than 50% of the surface of the porous structure based on glass fibers is coated. - The average coating thickness is greater than 0.5 pm and less than 300 pm.

[0010] The invention also relates to a method for manufacturing a three-dimensional structure coated according to the invention comprising the following steps: a. Production of a suspension comprising • particles of an adsorbent material chosen from MOFs, zeolites and their mixtures, • a polymer P chosen from a polyacrylate, an epoxy, a polyurethane, a polyimide, a polyamide and their mixtures, • a polysaccharide, • a solvent; b. Deposition of the suspension on the porous three-dimensional structure based on glass fibers; c. Drying.

[0011] Preferably, the manufacturing method according to the invention also has one or more of the following optional characteristics: - The polymer P is a polyacrylate and / or in which the polysaccharide is chosen from a cellulose, a cellulose derivative, a starch, a starch derivative and their mixtures. - The polysaccharide is chosen from a cellulose, a cellulose derivative and their mixtures, preferably is a carboxymethylcellulose. - The ratio of the mass of the polymer P to the mass of the polysaccharide is greater than or equal to 1 and preferably less than or equal to 15. - The ratio of the sum of the masses of polymer P and polysaccharide, to the sum of the mass of the particles of a material chosen from MOFs, zeolites and their mixtures, of the mass of polymer P and of the mass of polysaccharide, is greater than or equal to 1%, preferably greater than or equal to 5%, and less than or equal to 30%. - The maximum temperature reached during drying in step c) is greater than or equal to 20°C. - The particles contain MOF particles, and the maximum temperature reached during drying is lower than:

[0012] - the MOF degradation temperature minus 5°C or at the lowest temperature of degradation of MOFs less than 5°C, if the MOF degradation temperature less than 5°C or the lowest MOF degradation temperature less than 5°C is less than 200°C, or

[0013] - 200°C, if the MOF degradation temperature is less than 5°C or the lowest temperature MOF degradation temperature minus 5°C is greater than or equal to 200°C.

[0014] - The particles are chosen from zeolites, and the maximum temperature reached during drying in step c) is less than 200°C.

[0015] The invention finally relates to a device comprising a porous three-dimensional structure coated according to the invention or manufactured according to the method according to the invention, said device being chosen from a device for filtering a fluid, preferably chosen from a liquid and a gas, a device for storing a fluid, preferably chosen from a liquid and a gas, a catalyst support. Definitions

[0016] - According to the classical definition, "polysaccharides" are polymers composed of chains of osidic units linked by glycosidic bonds. - The term "degradation temperature of a MOF" refers to the temperature at which the last mass loss peak of the MOF begins (in other words, the peak occurring at the highest temperatures), as observed in thermogravimetric analysis (TGA). D / Detailed description

[0017] Three-dimensional porous structure coated according to the invention

[0018] Three-dimensional porous structure based on glass fibers

[0019] Preferably, the porous three-dimensional structure based on glass fibers is a monolith comprising at least one, preferably several channels, separated by walls based on glass fibers.

[0020] When the use of the three-dimensional porous structure based on glass fibers envisaged is the adsorption of molecules or to carry out separation, a fluid is intended to circulate inside the channels of said structure.

[0021] The porous three-dimensional structure based on glass fibers can be of any shape. Preferably, it is of substantially cylindrical shape, of length L.

[0022] The section may be square, rectangular or disc-shaped.

[0023] Preferably, the porous three-dimensional structure based on glass fibers comprises channels, preferably cylindrical, extending in the direction of the length L.

[0024] Preferably, the average thickness of the walls between the channels is greater than or equal to 0.1 mm, preferably greater than or equal to 0.2 mm and preferably less than or equal to 1 mm, preferably less than or equal to 0.8 mm, preferably less than or equal to 0.5 mm.

[0025] The number of channels per unit area, in a cross-section of the three-dimensional structure, is preferably greater than 3 / cm2, preferably greater than 5 / cm2 and preferably less than 80 / cm2, preferably less than 70 / cm2, preferably less than 60 / cm2.

[0026] Preferably, the section of a channel is greater than 0.5 mm2, preferably greater than 1 mm2, and preferably less than 20 mm2, preferably less than 15 mm2.

[0027] Preferably, the porous three-dimensional structure based on glass fibers contains more than 35%, preferably more than 40%, by mass percentage of glass fibers. Preferably, in said three-dimensional structure, the mass balance to the glass fibers consists of more than 90%, preferably more than 95%, of one or more compounds. The glass fibers constitute the skeleton of the three-dimensional structure, and are preferably linked by an organic and / or inorganic component, preferably one or more polymers, which makes it possible to ensure the connection between the glass fibers in the structure.

[0028] Preferably, the glass constituting the glass fibers of the porous three-dimensional structure has the following chemical composition, in percentage by mass SiO2: 50% - 85%, A12O3: < 18%, B2O3: < 10%, CaO + MgO: 5% - 28%, - Other elements: < 10%.

[0029] In a preferred embodiment, the porous three-dimensional structure based on glass fibers has a corrugation on at least part of its surface. Particles of an adsorbent material

[0030] The particles are particles made of an adsorbent material chosen from MOFs, zeolites and their mixtures.

[0031] The particles may comprise particles of an identical MOF. The particles may also comprise a mixture of particles of different MOFs, preferably of at least two different MOFs. Preferably, the MOF is chosen from MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-199, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-63, MIL-100, MIL101, ZIF-57, SUM-102, SUM-103 and mixtures thereof.

[0033] In one embodiment, in particular when the coated porous three-dimensional structure according to the invention is intended for use aimed at adsorbing CO2 and / or toluene, the MOF is chosen from MOF-199, UiO-66, HKUST-1, MIL-63, MIL-101, MIL-177, ZIF-57, and mixtures thereof.

[0034] Preferably, the median size of the MOF particles is greater than 0.1 pm and / or less than 100 pm.

[0035] Preferably, the degradation temperature of the MOF, or even of each MOF, is greater than 120°C, preferably greater than 130°C, preferably greater than 140°C. In one embodiment, the degradation temperature of the MOF, or even of each MOF, is less than 250°C, preferably less than 200°C.

[0036] The particles may comprise particles of an identical zeolite. The particles may also comprise a mixture of particles of different zeolites, preferably of at least two different zeolites.

[0037] Preferably, the zeolite, preferably all the zeolites are chosen from the zeolites of the FAU, MFI, LTA, MOR, BEA, FER families, and their mixtures.

[0038] In one embodiment, in particular when the porous three-dimensional structure coated according to the invention is intended for use aimed at adsorbing CO2 and / or toluene, the zeolite, preferably all the zeolites, are chosen from zeolites of the FAU, MFI families, and their mixtures.

[0039] In one embodiment, the particles of an adsorbent material are MOF particles.

[0040] In one embodiment, the particles of an adsorbent material are zeolite particles. Binder

[0041] The binder comprises, preferably consists essentially of, a crosslinked polymer chosen from a crosslinked polyacrylate, a crosslinked epoxide, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and mixtures thereof. Preferably, the binder consists of a crosslinked polymer chosen from a crosslinked polyacrylate, an epoxide crosslinked, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and mixtures thereof.

[0042] Preferably the binder comprises, preferably consists essentially of, a crosslinked polyacrylate. Preferably, the binder consists of a crosslinked polyacrylate. The crosslinked polyacrylate may be a substituted polyacrylate and / or an unsubstituted polyacrylate.

[0043] Preferably, the ratio of the quantity of binder to the sum of the mass of the particles of adsorbent material and the mass of binder is preferably greater than or equal to 1%, preferably greater than or equal to 3%, preferably greater than or equal to 4%, preferably greater than or equal to 5%, and preferably less than or equal to 30%, preferably less than 25%, preferably less than or equal to 20%, preferably less than or equal to 16%, preferably less than or equal to 12%. A ratio of the quantity of binder less than 30%, preferably less than 25%, to the sum of the mass of the particles of adsorbent material and the mass of binder, advantageously makes it possible to increase the quantity of particles of adsorbent material for an equivalent volume.

[0044] Three-dimensional porous structure coated according to the invention

[0045] Preferably, more than 50%, preferably more than 60%, preferably more than 70%, preferably more than 80%, preferably more than 85%, preferably more than 90%, preferably more than 95% of the surface of the porous glass fiber-based structure is coated with the coating comprising, preferably consisting of particles bound by a binder, said particles being essentially particles of an adsorbent material chosen from MOFs, zeolites and mixtures thereof, said binder comprising a crosslinked polymer chosen from a crosslinked polyacrylate, a crosslinked epoxide, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and mixtures thereof

[0046] In a preferred embodiment, substantially the entire surface of said porous three-dimensional glass fiber-based structure is coated with said coating.

[0047] Preferably, the average thickness of the coating is greater than 0.5 μm, preferably greater than 1 μm, preferably greater than 5 μm, preferably greater than 10 μm, preferably greater than 20 μm, preferably greater than 30 μm, preferably greater than 40 μm, preferably greater than 50 μm, preferably greater than 60 μm, preferably greater than 70 μm, preferably greater than 80 μm, and preferably less than 300 μm, preferably less than 200 μm, preferably less than 150 μm.

[0048] In one embodiment, the coated fiberglass porous three-dimensional structure is in the form of a monolith comprising channels, preferably cylindrical, extending in the length direction, and on a section of said porous three-dimensional structure, preferably on all sections, the ratio of the average of the surface area of ​​the coated channels to the average of the surface area of ​​the channels before coating is less than 0.95, preferably less than 0.9, preferably less than 0.86, and preferably greater than 0.1, preferably greater than 0.2, preferably greater than 0.3, preferably greater than 0.4, preferably greater than 0.5.

[0049] Preferably, said coated porous three-dimensional structure has a void volume fraction greater than 30%, the void volume fraction corresponding to the volume ratio between the void volume (space not occupied by the material of the three-dimensional structure) and the volume of the three-dimensional structure. Advantageously, the pressure drop is reduced.

[0050] Preferably the void volume fraction is greater than 40%, preferably greater than 50%, and preferably less than 95%, preferably less than 90%.

[0051] Method of manufacturing the coated porous three-dimensional structure according to the invention

[0052] In step a), a suspension is produced comprising particles of an adsorbent material chosen from MOFs, zeolites and their mixtures, a polymer P chosen from a polyacrylate, an epoxide, a polyurethane, a polyimide, a polyamide and their mixtures, a polysaccharide, and a solvent.

[0053] All the preferred characteristics for the MOFs and zeolites used for the coated glass fiber porous three-dimensional structure are also preferred characteristics for the MOF and / or zeolite particle(s) of step a).

[0054] Preferably, the polymer P is a polyacrylate. The polyacrylate may be a substituted polyacrylate and / or an unsubstituted polyacrylate.

[0055] Preferably, the polysaccharide, which makes it possible to crosslink the polymer P, preferably the polyacrylate, is chosen from a cellulose, a cellulose derivative, a starch, a starch derivative and their mixtures. Preferably, the polysaccharide is chosen from a cellulose, a cellulose derivative and their mixtures.

[0056] More preferably, the polysaccharide is a carboxymethylcellulose.

[0057] The ratio of the mass of the polymer P to the mass of the polysaccharide is preferably greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 3, and preferably less than or equal to 15, preferably less than or equal to 10, preferably less than or equal to 8.

[0058] Preferably, the ratio of the sum of the masses of polymer P and polysaccharide, to the sum of the mass of the particles of adsorbent material, of the mass of polymer P and of the mass of polysaccharide, is preferably greater than or equal to 1%, preferably greater than or equal to 3%, preferably greater than or equal to 4%, preferably greater than or equal to 5%, and preferably less than or equal to 30%, of preferably less than or equal to 25%, preferably less than or equal to 20%, preferably less than or equal to 16%, preferably less than or equal to 12%.

[0059] Preferably, the solvent is water. The amount of solvent is adapted to the deposition process implemented during step b).

[0060] The suspension may comprise, in addition to the particles of an adsorbent material, the polymer P, the polysaccharide and the solvent, a plasticizer and / or a lubricant, the nature and quantities of which are adapted to the deposition process implemented during step b).

[0061] The mixing of the different constituents can be carried out according to any technique known to those skilled in the art, for example in a mixer, preferably in a high-intensity mixer or in a Z-arm mixer, in a turbulator, in a jar mill with balls, preferably alumina balls. Preferably, the mixing is carried out in a high-intensity mixer or in a Z-arm mixer.

[0062] The total mixing time is preferably greater than 5 minutes, and preferably less than 30 minutes, preferably less than 20 minutes.

[0063] In step b), the suspension is deposited on the porous three-dimensional structure based on glass fibers using any technique known to those skilled in the art, such as dip coating, pressure infiltration or vacuum infiltration.

[0064] Preferably, the suspension is deposited on the porous three-dimensional structure based on glass fibers by dip coating.

[0065] The number of dips of the three-dimensional structure is determined so as to deposit the target quantity of suspension.

[0066] In step c), the three-dimensional structure obtained at the end of step b) is dried.

[0067] Preferably, the maximum temperature reached during said drying is greater than or equal to 20°C, preferably greater than or equal to 40°C, preferably greater than or equal to 50°C, preferably greater than or equal to 70°C, preferably greater than or equal to 80°C.

[0068] In one embodiment, the particles of adsorbent material comprise MOF particles, and preferably the maximum temperature reached during drying is less than:

[0069] - the MOF degradation temperature minus 5°C or at the lowest temperature of degradation of MOFs less than 5°C, preferably less than the MOF degradation temperature less than 10°C or the lowest MOF degradation temperature less than 10°C, if the MOF degradation temperature less than 5°C or the lowest MOF degradation temperature less than 5°C is less than 200°C, or

[0070] - 200°C, preferably less than or equal to 150°C, preferably less than or equal at 130°C, preferably less than or equal to 100°C, if the degradation temperature of the MOF minus 5°C or the lowest degradation temperature of the MOFs minus 5°C is greater than or equal to 200°C.

[0071] This embodiment is particularly well suited when the polymer P chosen in step a) is a polyacrylate.

[0072] In one embodiment, the particles of adsorbent material are chosen from zeolites, and preferably the maximum temperature reached during drying is less than 200°C, preferably less than or equal to 150°C, preferably less than or equal to 130°C, preferably less than or equal to 100°C. This embodiment is particularly well suited when the polymer P chosen in step a) is a polyacrylate.

[0073] More preferably, the drying cycle has a plateau at said maximum temperature reached. The holding time at the plateau is preferably greater than 1 hour, preferably greater than 2 hours, preferably greater than 5 hours, or even greater than 10 hours, and preferably less than 30 hours, or even less than 20 hours, or even less than 15 hours. Drying is preferably carried out in air, at atmospheric pressure.

[0074] When the particles of adsorbent material used in step a) are particles of MOF UiO-66, the degradation temperature of said MOF being substantially equal to 400°C, the maximum temperature reached during step c) is preferably less than 200°C, preferably less than or equal to 150°C, preferably less than or equal to 130°C, preferably less than or equal to 100°C, in particular when the polymer P chosen in step a) is a polyacrylate. Examples

[0075] The following non-limiting examples are given for the purpose of illustrating the invention. Measurement protocol

[0076] For each example, the amount of coating deposited on the porous three-dimensional structure of the examples, in kg / m3, is measured by the following method. The dimensions of the porous three-dimensional structure are measured so as to determine its overall volume, V, in m3.

[0077] The masses of the porous three-dimensional structure before deposition of the coating, M;, and after deposition of the coating, Mf are measured by weighing, in kilograms, after drying at 100°C for 14 hours.

[0078] The amount of coating deposited is equal to (Mr MO / V, in kg / m3. Manufacturing protocol

[0079] The following raw materials were used for the manufacture of the examples. - a MOF HKUST-1 powder, marketed by the company BASF, having a median size equal to 9 pm, for examples 1 and 3 excluding invention, and 2 according to the invention, - a FAU zeolite powder, NaMSXK / 13XBFK, marketed by the company CWK, having a median size equal to 3 pm, for examples 4 and 6 outside the invention, and 5 according to the invention, - an emulsion of Rhoplex GL-618 polyacrylate marketed by the company Dow, for examples 1 and 4 outside the invention, and for examples 2 and 5 according to the invention, - a sodium carboxymethylcellulose powder marketed by the company Thermo Fisher Scientific for examples 1 and 4 outside the invention, and for examples 2 and 5 according to the invention, - a Disperal P2 boehmite powder, marketed by the company SASOL, for examples 3 and 6 outside the invention,- a porous three-dimensional structure made of cordierite, a photo of which is described in [Fig.l], marketed by the company Hulteberg Chemistry & Engineering AB, having a diameter equal to 25.4 mm and a length equal to 25.4 mm, cylindrical channels of square section extending in the lengthwise direction, the number of channels being equal to 62 / cm2, the average thickness of the walls between the channels being equal to 0.18 mm and the average section of the channels being equal to 1.69 mm2, for examples 1 and 4 outside the invention, - a porous three-dimensional structure based on glass fibers, a photo of which is described in [Fig.2], having a square section with a side length equal to 25.4 mm and a length equal to 25.4 mm, cylindrical channels of triangular section extending in the length direction, the number of channels being equal to 40 / cm2, consisting of a stack of glass fiber mats and corrugated glass fiber mats, said mats having a thickness substantially equal to 0.2 mm, the pitch of the corrugations being equal to 3.2 mm and the height of said corrugations being equal to 1.5 mm, for examples 2 and 5 according to the invention, and for examples 3 and 6 outside the invention.

[0080] Suspension A used for Examples 1, 2, 4 and 5 was prepared in the following manner. 21.3 g of an emulsion of Rhoplex GL-618 are mixed in 40 ml of a 5% by mass aqueous solution of sodium carboxymethylcellulose using a paddle stirrer, then 348 g of distilled water are added. 100 g of a powder of particles of an adsorbent material (MOF HKUST-1 for Examples 1 and 2, and zeolite powder NaMSXK / 13XBFK for Examples 5 and 6) are then added and the whole is kept stirring for 1 hour. A homogeneous suspension is then obtained. The ratio of the mass of polyacrylate to the mass of sodium carboxymethylcellulose is equal to 5. The ratio of the sum of the masses of polyacrylate and sodium carboxymethylcellulose, to the sum of the mass of poly- acrylate, the mass of sodium carboxymethylcellulose and the mass of adsorbent material particles, expressed as a percentage, is equal to 11.

[0081] Suspension B used for Examples 3 and 6 was prepared in the following manner. 10 g of Disperal P2 boehmite are mixed in 312 g of distilled water using a paddle stirrer, then 0.57 g of a 70% by mass nitric acid solution are added. 100 g of a powder of particles of an adsorbent material (MOF HKUST-1 for Example 3, and zeolite NaMSXK / 13XBFK for Example 6) are then added and the whole is kept stirring for 1 hour. A homogeneous suspension is then obtained.

[0082] For each example, the porous three-dimensional structure is then dipped into the suspension, so as to deposit the suspension on the surface of the channels of said porous three-dimensional structure by dip coating. The number of dips is indicated in Table 1, drying at a temperature equal to 100°C for 14 hours being carried out between each dip.

[0083] For each example, the coated porous three-dimensional structure is then dried in air, at atmospheric pressure, at a temperature equal to 100°C for a time of 14 hours.

[0084] In Table 1, the “maximum quantity of coating deposited” corresponds to the quantity of coating deposited after dipping T for which less than 30% in number of the channels are blocked by said coating, the coating obtained after dipping T+1 blocking more than 30% in number of the channels of the porous three-dimensional structure.

[0085] The following Table 1 summarizes the results obtained.

[0086] [Tables 1] Examples 1(*) 2 3(*) 4(*) 5 6(*) Porous three-dimensional structure Cordierite Glass fiber based Glass fiber based Cordierite Glass fiber based Glass fiber based Suspension used AABAAB Adsorbent material particles MOF HKUST-1 Zeolite NaMSXK / 13XBFK Binder present in the coating on the surface of the coated porous three-dimensional structure, after drying Cross-linked polyacrylate Boehmite Cross-linked polyacrylate Boehmite Quantity of binder, based on the mass of adsorbent material particles and the mass of binder (%) 11 11 9 11 11 9 Maximum amount of coating deposited, measured after drying (kg / m3) 160 250 95 330 515 330 Number of dips required to obtain the maximum amount of coating deposited 7 9 4 6 6 4 Quantity of coating deposited, after 7 soaks, 160 210 - - - - measured after drying (kg / m3)

[0087] (*): outside the invention

[0088] A comparison of the coated three-dimensional porous structures of Examples 1 and 2 shows that the maximum amount of coating consisting of MOF HKUST-1 particles and crosslinked polyacrylate, measured after drying, is 56% greater for a three-dimensional porous structure based on glass fibers (250 kg / m3) than for a three-dimensional porous structure made of cordierite (160 kg / m3). The same observation can be made by comparing the amount of coating on the surface of the coated three-dimensional porous structure, after 7 dippings: it is 31% greater for a three-dimensional porous structure based on glass fibers (210 kg / m3) than for a three-dimensional porous structure made of cordierite (160 kg / m3).

[0089] A comparison of the coated three-dimensional porous structures of Examples 2 and 3 shows that the maximum amount of coating, measured after drying, covering a three-dimensional porous structure based on glass fibers is 163% greater for a crosslinked polyacrylate binder (250 kg / m3) than for a boehmite binder (95 kg / m3). The same observation can be made by comparing the amount of coating on the surface of the coated three-dimensional porous structure, after 7 dippings: it is 121% greater for a crosslinked polyacrylate binder (210 kg / m3) than for a boehmite binder (95 kg / m3).

[0090] The CO2 adsorption capacity of the coating materials of the porous structures of the examples is measured conventionally using thermogravimetric analysis, at a temperature equal to 50°C, under a gas flow composed by volume of 50% helium and 50% CO2, injected at a flow rate of 3 liters per hour, the quantity of the coating materials of the porous structures of the examples being between 0.1 g and 0.2 g, said materials being the suspension obtained at the end of step a) of the process according to the invention and dried at 100°C for 14 hours. The samples are again dried at 100°C for 1 hour under helium, in the thermogravimetric apparatus immediately before the capacity measurement.

[0091] During the measurement, the mass gain of the sample corresponds to the quantity of CO2 adsorbed by it. The result is expressed in mg of CO2 per gram of adsorbent product contained in the characterized coating material.

[0092] The inventors found by this method that the CO2 adsorption capacity of the MOF HKUST-1 particles was not modified by the presence of the crosslinked polyacrylate binder.

[0093] A comparison of the coated three-dimensional porous structures of Examples 4 and 5 shows that the maximum amount of coating consisting of particles of NaMSXK / 13XBFK zeolite and crosslinked polyacrylate, measured after drying, is 56% greater for a three-dimensional porous structure based on glass fibers (515 kg / m3) than for a three-dimensional porous structure in cordierite (330 kg / m3).

[0094] A comparison of the coated three-dimensional porous structures of Examples 5 and 6 shows that the maximum amount of coating, measured after drying, covering a three-dimensional porous structure based on glass fibers is 56% greater for a crosslinked polyacrylate binder (515 kg / m3) than for a boehmite binder (330 kg / m3).

[0095] These results show that, surprisingly, there is a synergy between a three-dimensional porous structure based on glass fibers and a coating whose binder is a crosslinked polyacrylate: the quantity of coating on the surface of said three-dimensional porous structure is advantageously increased, in particular before the channels are blocked, which makes it possible to increase the quantity of active material for the same volume, thereby improving the performance of the covered three-dimensional porous structure.

[0096] Of course, the invention is not limited to the embodiments described, provided only for illustration purposes.

Claims

Claims

1. Porous three-dimensional structure based on glass fibers, coated at least partially with a coating comprising particles bound by a binder, preferably consisting of particles bound by a binder, said particles being essentially particles of a material chosen from MOFs, zeolites and their mixtures, said binder comprising a crosslinked polymer chosen from a crosslinked polyacrylate, a crosslinked epoxide, a crosslinked polyurethane, a crosslinked polyimide, a crosslinked polyamide and their mixtures.

2. A coated porous three-dimensional structure according to the preceding claim, wherein the porous three-dimensional structure based on glass fibers is a monolith comprising at least one channel, preferably several channels separated by walls.

3. A coated porous three-dimensional structure according to the preceding claim, wherein the number of channels per unit area, in a cross-section of said three-dimensional structure is greater than 3 / cm2 and less than 80 / cm2.

4. A coated porous three-dimensional structure according to any preceding claim, wherein the glass fiber-based porous three-dimensional structure contains more than 35% glass fibers, by mass percentage.

5. A coated porous three-dimensional structure according to any preceding claim, wherein the glass fiber-based porous three-dimensional structure has corrugation on at least a portion of its surface.

6. A coated porous three-dimensional structure according to any preceding claim, wherein the MOF is selected from MOF-O, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-199, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-63, MIL-100, MIL101, ZIF-57, SUM-102, SUM-103 and mixtures thereof, and the zeolite is selected from the zeolites of the FAU, MFI, LT A, MOR, BEA, FER families, and mixtures thereof.

7. A coated porous three-dimensional structure according to any preceding claim, wherein the particles are MOF particles.

8. A coated porous three-dimensional structure according to any one of claims 1 to 6, wherein the particles are zeolite particles.

9. A coated porous three-dimensional structure according to any preceding claim, wherein the binder comprises a crosslinked polyacrylate, preferably consists of a crosslinked polyacrylate.

10. A coated porous three-dimensional structure according to any preceding claim, wherein the ratio of the amount of binder, to the sum of the mass of the MOF and zeolite particles and the mass of binder, is greater than or equal to 1% and less than or equal to 30%.

11. Coated porous three-dimensional structure according to the preceding claim, in which the ratio of the quantity of binder, to the sum of the mass of the MOF and zeolite particles and the mass of binder, is greater than or equal to 5%.

12. A coated porous three-dimensional structure according to any preceding claim, wherein more than 50% of the surface area of ​​the glass fiber porous structure is coated.

13. A coated porous three-dimensional structure according to any preceding claim, wherein the average thickness of the coating is greater than 0.5 µm and less than 300 µm.

14. Method for manufacturing a coated three-dimensional structure according to any one of the preceding claims, comprising the following steps: a. Production of a suspension comprising particles of a material chosen from MOFs, zeolites and their mixtures, a polymer P chosen from a polyacrylate, an epoxide, a polyurethane, a polyimide, a polyamide and their mixtures, a polysaccharide, a solvent; b. Deposition of the suspension on the porous three-dimensional structure based on glass fibers; c. Drying.

15. Manufacturing method according to the preceding claim, in which the polymer P is a polyacrylate and / or in which the polysaccharide is chosen from a cellulose, a cellulose derivative, a starch, a starch derivative and their mixtures.

16. Manufacturing method according to the preceding claim, in the polysaccharide is chosen from a cellulose, a cellulose derivative and their mixtures, preferably is a carboxymethylcellulose.

17. Manufacturing process according to any one of claims 14 to 16, in which the ratio of the mass of the polymer P to the mass of the polysaccharide is greater than or equal to 1 and preferably less than or equal to 15.

18. 1 J. Manufacturing method according to any one of claims 14 to 17, in which the ratio of the sum of the masses of polymer P and polysaccharide, to the sum of the mass of the particles of a material chosen from MOFs, zeolites and their mixtures, of the mass of polymer P and of the mass of polysaccharide, is greater than or equal to 1% and less than or equal to 30%.

19. Manufacturing method according to any one of claims 14 to 18, wherein the maximum temperature reached during drying in step c) is greater than or equal to 20°C.

20. A manufacturing method according to any one of claims 14 to 19, wherein the particles comprise MOF particles, and the maximum temperature reached during drying is less than: - the MOF degradation temperature minus 5°C or the lowest MOF degradation temperature minus 5°C, if the MOF degradation temperature minus 5°C or the lowest MOF degradation temperature minus 5°C is less than 200°C, or - 200°C, if the MOF degradation temperature minus 5°C or the lowest MOF degradation temperature minus 5°C is greater than or equal to 200°C.

21. Manufacturing process according to any one of claims 14 to 19, in which the particles are chosen from zeolites, and the maximum temperature reached during drying in step c) is lower

22. at 200°C. Device comprising a porous three-dimensional structure coated according to any one of claims 1 to 13 or manufactured according to a method according to the invention any one of claims 14 to 21, said device being chosen from a fluid filtration device, a fluid storage device, a catalyst support.

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