WO2014135783A1 - Method for producing a hybrid organic-inorganic material shaped using a polymer binder - Google Patents

Method for producing a hybrid organic-inorganic material shaped using a polymer binder Download PDF

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Publication number
WO2014135783A1
WO2014135783A1 PCT/FR2014/050474 FR2014050474W WO2014135783A1 WO 2014135783 A1 WO2014135783 A1 WO 2014135783A1 FR 2014050474 W FR2014050474 W FR 2014050474W WO 2014135783 A1 WO2014135783 A1 WO 2014135783A1
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Prior art keywords
weight
organic
inorganic hybrid
powder
polymer
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PCT/FR2014/050474
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French (fr)
Inventor
Delphine Bazer-Bachi
Serge Gonzalez
Bogdan Harbuzaru
Jacques Vallet
Laetitia ASSIE
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IFP Energies Nouvelles
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Priority to EP14713526.3A priority Critical patent/EP2964697A1/en
Publication of WO2014135783A1 publication Critical patent/WO2014135783A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase

Definitions

  • the present invention relates to the field of crystalline organic-inorganic hybrid materials (MHOIC) and, in particular, that of their shaping for use in industrial applications for catalysis, storage for example of gas, or the separation. More specifically, this invention relates to a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of an organic hybrid material. inorganic crystalline material and the process for preparing said novel material, said method comprising at least one step of mixing at least one powder of at least one crystalline organic-inorganic hybrid material with at least one powder of at least one polymer.
  • MHOIC crystalline organic-inorganic hybrid materials
  • crystallized organic-inorganic hybrid materials are understood to mean any crystallized material containing organic and inorganic entities (atoms, clusters) connected by chemical bonds.
  • MOF Metal Organic Framework according to the English terminology
  • coordination polymers ZIFs (or Zeolitic Imidazolate Frameworks according to the English terminology)
  • MILs or Materials of the Lavoisier Institute
  • IRMOFs or IsoReticular Metal Organic Framework according to the English terminology.
  • organic-inorganic mixed matrix porous hybrid materials are quite similar to porous inorganic skeleton materials. Like the latter, they associate chemical entities by giving rise to porosity. The main difference lies in the nature of these entities. This difference is particularly advantageous and is at the origin of all the versatility of this category of hybrid materials. Indeed, the size of the pores becomes, through the use of organic ligands, adjustable through the length of the carbon chain of said organic ligands.
  • the framework which in the case of inorganic porous materials, can accept only a few elements (Si, Al, Ge, Ga, P possibly Zn) can, in this case, accommodate the majority of the cations.
  • the solvent (and / or the ligand) plays this effect alone.
  • the crystallized organic-inorganic hybrid materials comprise at least two elements called connectors and ligands whose orientation and the number of binding sites are determinants in the structure of said hybrid material. From the diversity of these natt ligands and connectors, as already mentioned, an immense variety of hybrid materials.
  • Connector means the inorganic entity of said hybrid material. It can be a single cation, a dimer, trimer or tetramer or a chain or a plane.
  • the teams of Yaghi and Férey have thus described a large number of new hybrid materials (series of MOFs - "Metal Organic Framework” - and series of MIL - “Materials of the Lavoisier Institute” - respectively). Many other teams have followed this path and today the number of new hybrid materials described is expanding. Most often, the studies are aimed at developing ordered structures with extremely large pore volumes, good thermal stability, and adjustable chemical functionality.
  • Yaghi et al. disclose a series of boron structures in US patent application 2006/0154807 and indicate their interest in the field of gas storage.
  • US Pat. No. 7,202,385 discloses a particularly complete summary of the structures described in the literature and perfectly illustrates the multitude of hybrid materials existing to date.
  • MHOIC crystalline organic-inorganic hybrid materials
  • MHOIC crystalline organic-inorganic hybrid materials
  • Finsy et al. (Finsy et al., Separation of CO 2 / CH 4 mixtures vvith the MIL53 (AI) metal-organic framework, Microporous and mesoporous materials, 120 (2009) 221-227) describes the preparation of MIL-53 materials shaped by stirring evaporation of the solvent in which the polymer (polyvinyl alcohol PVA, present at a level of 13% by weight relative to the total mass of the material) was previously dissolved and studied the column separation properties of the agglomerates obtained. Finsy et al. describes the preparation of objects of size between 500 and 630 microns. No details on the mechanical properties of obtained granules and in particular on the crush resistance is provided but it is observed that the reduction of the microporous volume is 32% after activation at 190oC.
  • the polymer polyvinyl alcohol PVA
  • Patent Application US2003 / 0222023A1 discloses shaped materials of the MOF type prepared by shaping a composition comprising a crystallized organic-inorganic hybrid material and a binder. All shaping techniques are described: pelletizing, kneading, extrusion, granulation, etc.
  • the materials described as binders in the text are inorganic compounds, minerals such as silica, alumina, clay or graphite and organic compounds such as silanes.
  • Hydrophilic polymers such as PVA (polyvinyl alcohol) and PVP (polyvinylpyrrolidone) are cited as a thickener of the preparation prior to shaping.
  • the examples of the application US2003 / 0222023A 1 mention only the shaping of such materials by pelletizing.
  • the materials obtained have a crush strength of 2 to 100 N.
  • US Pat. No. 3,737,983B1 discloses membranes comprising a continuous polymer organic phase and a crystallized organic-inorganic hybrid material dispersed in the continuous polymer phase, their method of preparation and a process for separating gas by bringing a gas into contact with said membrane .
  • the membranes are prepared by mixing a polymer solution with a crystalline organic-inorganic hybrid material powder to form a dispersion and the mixture is then cast to form a membrane.
  • the examples of US Pat. No. 3,737,983 mention membranes containing 20 to 30% of hybrid organic-inorganic material crystallized with a polyimide matrix (Matrimid, Ultem).
  • the patent application WO 201 1/100501 A1 also describes composite membranes intended for the separation of gases.
  • the membrane consists of an organometallic phase and a polymeric phase.
  • the self associative polymers (organization by non-covenant bonds: hydrogen bond, ionic, intermolecular) are described.
  • the compositions contain from 1 to 70% by weight of crystallized organic-inorganic hybrid material.
  • Chapter 15 of the book "Metal-Organic Frameworks: Applications from Catalysis to Gas Storage” published by Wiley takes the techniques of shaping hybrid organic-inorganic material crystallized according to the intended applications.
  • An object of the present invention is to provide a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of one crystallized organic-inorganic hybrid material,
  • Another object of the present invention is to provide a new process for preparing said material comprising at least one crystallized organic-inorganic hybrid material (MHOIC) shaped as extrudates with a binder formulation comprising at least one polymer.
  • MHOIC crystallized organic-inorganic hybrid material
  • the present invention relates to a material comprising at least one crystallized organic-inorganic hybrid material shaped in the form of an extrusion with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystalline organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
  • the present invention also relates to a process for preparing said material comprising at least the following steps:
  • MHOIC crystalline organic-inorganic hybrid material
  • An advantage of the present invention is to provide a material and its preparation process allowing its shaping with a content of high crystallized organic-inorganic hybrid material and in particular between 80 and 99% by weight relative to the mass of the material, said obtained material having both a good mechanical strength and a loss of microporous volume with respect to the porosity of the starting crystallized organic-inorganic hybrid material limited.
  • the material thus obtained is suitable for use in an industrial process over long periods.
  • the material according to the present invention comprises at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
  • the crystalline organic-inorganic hybrid material (s) used (MHOIC) used in the material according to the present invention are preferably selected from the MOF (Metal Organic Framework according to US Pat. English terminology), the ZlFs (or Zeolitic Imidazolate Frameworks according to the English terminology), the MILs (or Materials of the Lavoisier Institute), the IRMOFs (or isoReticular Metal Organic Framework according to the English terminology), only or in mixture.
  • MOF Metal Organic Framework according to US Pat. English terminology
  • ZlFs or Zeolitic Imidazolate Frameworks according to the English terminology
  • MILs or Materials of the Lavoisier Institute
  • IRMOFs or isoReticular Metal Organic Framework according to the English terminology
  • said crystalline organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from the following list: 1, HKUST, CAU-1, MOF-5, MOF-38, MOF-305, MOF-37, MOF-12, IRMOF-2 to -16, MIL-53, MIL-68, MIL-101, ZIF-8 , ZIF-1 1, ZIF-67, ZIF-90, alone or in admixture.
  • the said hybridized organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from SIM-1, HKUST and ZIF-8, alone or mixed.
  • the said crystallized organic-inorganic hybrid material (s) (MHOIC) are used in step a) of the preparation process according to the invention in powder form.
  • the said (s) binder (s) polymer (s) is (are) advantageously chosen (s) among the polymers well known to those skilled in the art.
  • the said polymer (s) is (are) chosen from polyvinylpyrrolidones, cellulosic polymers and their derivatives, preferably chosen from cellulose ethers such as, for example, Methocel, sold by Dow Chemical, polyvinyl alcohols, polyethylene glycols, polyacrylamides, polysaccharides, natural polymers and their derivatives such as, for example, alginates, polyesters, polyamides and aromatic polyamides, polyethers poly (aryether), polyurethanes, polysulfones such as polyether sulfones, heterocylic polymers, preferably selected from polyimides, polyether imides, polyesters imides, polyamide imides, and polybenzimidazoles.
  • the said binder (s) polymer (s) is (are) chosen from polyvinylpyrrolidones, heterocyclic polymers and cellulosic polymers and very preferably from polyvinylpyrrolidones, polyimides and cellulose ethers.
  • polymer By polymer is meant a compound having at least 20 repeating units or a molecular weight greater than 500 g.mol -1 .
  • said material consists of 85 to 99% by weight of at least one crystallized organic-inorganic hybrid material and 1 to 15% by weight of at least one polymeric binder, and preferably from 90 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 10% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
  • said material is in the form of extrudates.
  • said material is in the form of extrudates with a diameter of between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
  • Said materials according to the invention having a high content of crystallized organic-inorganic hybrid material have increased mechanical properties, especially in terms of mechanical strength, regardless of the content used, and are resistant to a rise in moderate temperature, which allows to consider the implementation of said material in processes at relatively high temperatures but still limited by the temperature resistance of the hybrid organic-inorganic crystalline material (MHOIC) and / or the polymer.
  • MHOIC crystallized organic-inorganic hybrid material
  • Said materials according to the invention can therefore be used for applications in catalysis and separation.
  • said materials according to the invention have a mechanical resistance measured by the grain-to-grain crushing test, noted by EGG at least greater than 0.4 daN / mm and preferably at least greater than 0.9 daN / mm and preferably at least greater than 1 daN / mm.
  • the mechanical strength of the material according to the invention determined by the grain-to-grain (GGE) crushing test.
  • GGE grain-to-grain
  • ASTM D4179-01 standardized test that involves subjecting a material as a millimeter object, such as a ball, pellet, or extrusion, to a compressive force that causes the breakage. This test is therefore a measure of the tensile strength of the material. The analysis is repeated on a number of solids taken individually and typically on a number of solids between 10 and 200.
  • the average of the lateral forces of rupture measured constitutes the average EGG which is expressed in the case of the granules in unit of force (N), and in the case of extrusions in unit of force per unit length (daN / mm or decaNewton per millimeter of extruded length).
  • said materials according to the invention exhibit a loss of microporous volume of less than 35%, preferably less than 30%, preferably less than 25 and more preferably less than 15%.
  • the loss of micro porosity is calculated taking into account the dilution due to the presence of polymer binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder. starting point, weighted with the dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in extruded form.
  • the loss of microporosity [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x% by mass of MHOIC present in the final material obtained in extruded form) / 100).
  • the present invention also relates to a process for the preparation of said material according to the invention.
  • the method of preparing the material comprising at least the following steps: a) a step of mixing at least 80 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) with at least 1 to 20% by weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a), b) a step of extrusion shaping of the mixture obtained at the end of step a), c) a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C., for a period of time between 1 minute and 72 hours.
  • MHOIC crystalline organic-inorganic hybrid material
  • the sum of the amounts of each of the powders introduced in said step a) is equal to 100%.
  • said step a) consists of mixing at least 80 to 99% by weight and preferably at least 85 to 99% by weight and preferably at least 90 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC), with at least 1 to 20% by weight and preferably with at least 1 to 15% by weight and more preferably at least 1 to 10% by weight of a powder of at least one polymer and a solvent to obtain a mixture.
  • MHOIC crystallized organic-inorganic hybrid material used in powder form in the process for preparing the material according to the present invention and the polymers are described. upper.
  • Said solvent is advantageously chosen from water, the alcohols preferably chosen from ethanol and methanol, amines, ethers, esters, ketones, lactones, phenols, cresols, polar aprotic solvents such as DMF, DMAC, NMP for example.
  • the polymer (s) may be mixed in powder form or in solution in said solvent.
  • the order in which the mixture of the powders of at least one crystalline organic-inorganic hybrid material (MHOIC), at least one polymer and the solvent is produced is indifferent.
  • the mixture of said powders and of said solvent can advantageously be produced at one time.
  • said powders of at least one crystalline organic-inorganic hybrid material (MHOIC), of at least one polymer, in the case where they are mixed in the form of powders, are firstly prepared. -mixed, dry, before the introduction of the solvent.
  • MHOIC crystalline organic-inorganic hybrid material
  • the polymers may previously be in solution or suspension in said solvent when said solvent is brought into contact with the powders of at least one crystalline organic-inorganic hybrid material (MHOIC). Contacting with said solvent leads to obtaining a mixture which is then kneaded.
  • MHOIC crystalline organic-inorganic hybrid material
  • said mixing step a) is carried out by mixing, batchwise or continuously.
  • said step a) is advantageously carried out in a kneader preferably equipped with Z-arms, or with cams, or in any other type of mixer such as for example a planetary mixer, Said step a) of mixing makes it possible to obtain a homogeneous mixture of powder constituents and of the solvent,
  • said step a) is carried out for a period of between 5 and 60 minutes, and preferably between 10 and 50 minutes.
  • the rotation speed of the kneader arms is advantageously between 10 and 75 revolutions / minute. preferred way between 25 and 50 rpm.
  • said step b) consists in shaping by extrusion of the mixture obtained at the end of step a) of mixing.
  • Said step b) is advantageously carried out in a piston, single-screw or twin-screw extruder.
  • an organic adjuvant may optionally be added in the mixing step a). The presence of said organic adjuvant facilitates extrusion shaping.
  • said mixing step a) can be coupled with the extrusion shaping step b) in the same equipment.
  • the extrusion of the mixture also called “kneaded paste” can be carried out either by directly extruding the end of continuous twin-screw kneader for example, or by connecting one or more batch kneaders to an extruder.
  • the geometry of the die, which confers their shape to the extrudates can be chosen from the well-known dies of the skilled person. They can thus be, for example, cylindrical, multilobed, fluted or slotted.
  • step a) the amount of solvent added in step a) of mixing is adjusted so as to obtain, at the end of this step and whatever the variant used, a mixture or a paste that does not flow but is not too dry to allow its extrusion under suitable conditions of pressure and temperature well known to those skilled in the art and dependent on the extrusion equipment used.
  • said extrusion forming step b) is carried out at an extrusion pressure greater than 1 MPa and preferably between 3 MPa and 10 MPa.
  • said step c) consists of a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C, preferably between 25 and 200 ° C and preferably between 25 and 150 ° C for a period of between 1 minute and 72 hours, preferably between 30 minutes and 72 hours, and preferably between 1 hour and 48 h and more preferably between 1 and 12 h.
  • Said heat treatment step is preferably a maturation step and can advantageously be carried out under inert gas or under vacuum.
  • said maturation step is carried out under air.
  • the material obtained is in the form of extrudates of size between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
  • said materials obtained are then, for example, introduced into equipment for rounding their surface, such as a bezel or other equipment allowing their spheronization.
  • Said method of preparation according to the invention makes it possible to obtain materials according to the invention having mechanical strength values measured by grain-to-grain crushing greater than 0.4 daN / mm, preferably greater than 0.9 daN / mm and preferably greater than 1 daN / mm, regardless of the content of (MHOIC) implemented.
  • the material obtained at the end of the preparation process according to the invention can be used for applications in catalysis, separation, purification, capture ...
  • Said material is brought into contact with the gaseous feedstock to be treated in a reactor, which can be either a fixed bed reactor, a radial reactor, or a fluidized bed reactor.
  • the expected EGG value is greater than 0.9 daN.mm -1 , preferably greater than 1.0 daN.mm -1 .
  • the viscous paste is introduced into a hand extruder (3 mm diameter die) and a sufficient pressure is applied to obtain a rod which is cut into extrudates of 1 cm in length.
  • the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
  • the viscous paste is introduced into a hand extruder (die ⁇ 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length.
  • the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
  • a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 8.25% by weight expressed relative to the total amount of powders introduced into said stage are introduced into a glass reactor equipped with mechanical stirring. a)) and 3.64 g of methanol. The mixture is stirred until complete solubilization of the polymer and 4 g of a ZIF-8 powder (Basolite Z1200) (representing 91.75% by weight relative to the total amount of powders introduced in said step a) are added. Stirring is then continued until a suspension assimilated to a viscous paste is obtained.
  • PVP polyvinylpyrrolidone
  • the viscous paste is introduced into a hand extruder (die ⁇ 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length.
  • Step a) 2 g of a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 10% by weight relative to the total amount of powders introduced in said step a) are introduced into a glass reactor equipped with mechanical stirring. ) and 19 ml of water. Stirring until complete solubilization of the polymer.
  • PVP polyvinylpyrrolidone
  • the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
  • the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. or 200 ° C. for 16 hours.
  • the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
  • the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. for 16 hours.
  • Step a) In a kneader equipped with cam shafts, 3.1 g of a K15M methocel powder marketed by DOW Chemicals (representing 5% by weight relative to the total quantity of powders introduced in said stage a)), 62.5 g (95% by weight relative to the total amount of powders introduced in said step a) of a SIM-I powder and 34.2 ml of water are mixed. The mixing is then continued until a paste is obtained.
  • a K15M methocel powder marketed by DOW Chemicals (representing 5% by weight relative to the total quantity of powders introduced in said stage a)
  • 62.5 g (95% by weight relative to the total amount of powders introduced in said step a) of a SIM-I powder and 34.2 ml of water are mixed. The mixing is then continued until a paste is obtained.
  • the paste is introduced into a capillary rheometer type piston extruder (die ⁇ 3 mm) and a sufficient pressure is applied to obtain a rod.
  • the extrudates are subjected to a heat treatment of 16 hours at 40 ° C. and then 120 ° C. for 16 hours.
  • the loss of microporosity is calculated taking into account the dilution due to the presence of polymeric binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder of starting, weighted dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in the form of extruded.
  • the loss of microporosity [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100).

Abstract

The invention relates to a novel composite material comprising at least one crystallised hybrid organic-inorganic material shaped in the form of an extruded product using a binder formulation comprising at least one polymer binder, said material having a high crystallised organic-inorganic hybrid material content. The invention also relates to the method for the production of said material.

Description

PROCEDE DE PRÉPARATION D'UN MATERIAU HYBRIDE ORGANIQUE- INORGANIQUE MIS EN FORME AVEC UN LIANT POLYMERE  PROCESS FOR THE PREPARATION OF ORGANIC-INORGANIC HYBRID MATERIAL SHAPED WITH POLYMER BINDER
La présente invention concerne le domaine des matériaux hybrides organique-inorganique cristallisés (MHOIC) et, en particulier, celui de leur mise en forme en vue d'une utilisation dans des applications industrielles pour la catalyse, le stockage par exemple de gaz, ou la séparation. Plus précisément cette invention concerne un nouveau matériau composite comprenant au moins un matériau hybride organique-inorganique cristallisé mis en forme sous forme d'extrudé avec une formulation liante comprenant au moins un liant polymère, ledit matériau présentant une teneur élevée en un matériau hybride organique-inorganique cristallisé et le procédé de préparation dudit nouveau matériau, ledit procédé comprenant au moins une étape de mélange d'au moins une poudre d'au moins un matériau hybride organique-inorganique cristallisé avec au moins une poudre d'au moins un polymère. The present invention relates to the field of crystalline organic-inorganic hybrid materials (MHOIC) and, in particular, that of their shaping for use in industrial applications for catalysis, storage for example of gas, or the separation. More specifically, this invention relates to a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of an organic hybrid material. inorganic crystalline material and the process for preparing said novel material, said method comprising at least one step of mixing at least one powder of at least one crystalline organic-inorganic hybrid material with at least one powder of at least one polymer.
Art antérieur Prior art
Dans toute la suite du texte, on entend par matériaux hybrides organique- inorganique cristallisés (MHOIC) tout matériau cristallisé contenant des entités organiques et inorganiques (atomes, clusters) reliées par des liaisons chimiques. Parmi cette classe de matériaux nous pouvons citer sans être exhaustifs les MOF (Métal Organic Framework selon la terminologie anglo-saxonne), les polymères de coordination, les ZIFs (ou Zeolitic Imidazolate Frameworks selon la terminologie anglo-saxonne), les MILs (ou Matériaux de l'Institut Lavoisier), les IRMOFs (ou IsoReticular Métal Organic Framework selon la terminologie anglo-saxonne). Lesdits matériaux hybrides organique-inorganique cristallisés (MHOIC) ont été décrits avec des premiers exemples dans les années 1960, et font l'objet d'un nombre croissant de publications. L'effervescence autour de ces matériaux a permis d'atteindre une diversité structurale avancée en peu de temps (Férey G., l'Actualité Chimique, janvier 2007, n°304). Conceptuel lement, lesdits matériaux hybrides poreux à matrice mixte organique-inorganique (MHOIC) sont assez semblables aux matériaux poreux à squelette inorganique. Comme ces derniers, ils associent des entités chimiques en donnant naissance à une porosité. La principale différence réside dans la nature de ces entités. Cette différence est particulièrement avantageuse et est à l'origine de toute la versatilité de cette catégorie de matériaux hybrides. En effet, la taille des pores devient, par l'utilisation de ligands organiques, ajustable par le biais de la longueur de la chaîne carbonée desdits ligands organiques. La charpente, qui dans le cas des matériaux poreux inorganiques, ne peut accepter que quelques éléments (Si, Al, Ge, Ga, P éventuellement Zn) peut, dans ce cas, accueillir la majorité des cations. Pour la préparation de ces matériaux hybrides, aucun agent structurant spécifique n'est requis, le solvant (et/ou le ligand) joue cet effet à lui seul. Throughout the rest of the text, crystallized organic-inorganic hybrid materials (MHOIC) are understood to mean any crystallized material containing organic and inorganic entities (atoms, clusters) connected by chemical bonds. Among this class of materials we can cite without being exhaustive the MOF (Metal Organic Framework according to the English terminology), coordination polymers, ZIFs (or Zeolitic Imidazolate Frameworks according to the English terminology), MILs (or Materials of the Lavoisier Institute), the IRMOFs (or IsoReticular Metal Organic Framework according to the English terminology). These crystalline organic-inorganic hybrid materials (MHOIC) have been described with early examples in the 1960s, and are the subject of an increasing number of publications. The effervescence around these materials made it possible to reach an advanced structural diversity in a short time (Férey G., Chemical News, January 2007, n ° 304). Conceptually, said organic-inorganic mixed matrix porous hybrid materials (MHOIC) are quite similar to porous inorganic skeleton materials. Like the latter, they associate chemical entities by giving rise to porosity. The main difference lies in the nature of these entities. This difference is particularly advantageous and is at the origin of all the versatility of this category of hybrid materials. Indeed, the size of the pores becomes, through the use of organic ligands, adjustable through the length of the carbon chain of said organic ligands. The framework, which in the case of inorganic porous materials, can accept only a few elements (Si, Al, Ge, Ga, P possibly Zn) can, in this case, accommodate the majority of the cations. For the preparation of these hybrid materials, no specific structuring agent is required, the solvent (and / or the ligand) plays this effect alone.
Il apparaît donc clairement que cette famille de matériaux hybrides organique-inorganique cristallisés permet une multiplicité de structures et par conséquent comprend des solides finement adaptés aux applications qui leur sont destinées.  It therefore clearly appears that this family of hybrid organic-inorganic crystallized materials allows a multiplicity of structures and therefore includes solids finely adapted to the applications intended for them.
Les matériaux hybrides organique-inorganique cristallisés (MHOIC) comprennent au moins deux éléments appelés connecteurs et ligands dont l'orientation et le nombre des sites de liaisons sont déterminants dans la structure dudit matériau hybride. De la diversité de ces ligands et connecteurs natt, comme on l'a déjà précisé, une immense variété de matériaux hybrides.  The crystallized organic-inorganic hybrid materials (MHOIC) comprise at least two elements called connectors and ligands whose orientation and the number of binding sites are determinants in the structure of said hybrid material. From the diversity of these natt ligands and connectors, as already mentioned, an immense variety of hybrid materials.
Par ligand, on désigne la partie organique dudit matériau hybride. Ces ligands sont, le plus souvent, des di- ou tri-carboxylates ou des dérivés azotés ou de la pyridine. Quelques ligands organiques fréquemment rencontrés sont représentés ci-après : bdc = benzène- 1 ,4- dicarboxylate, btc = benzène- 1 ,3,5-tricarboxylate, ndc = naphtaiène-2,6-dicarboxy!ate, bpy = 4,4'-bipyridine, hfipbb = 4,4'-(hexafluororisopropylidene)-bisbenzoate, cyclam = 1 ,4,8, 1 1 - tetraazacyclotetradecane, imz = imidazolates.  By ligand is meant the organic part of said hybrid material. These ligands are, most often, di- or tri-carboxylates or nitrogen derivatives or pyridine. Some organic ligands frequently encountered are represented below: bdc = benzene-1,4-dicarboxylate, btc = benzene-1,3,5-tricarboxylate, ndc = naphthalene-2,6-dicarboxyate, bpy = 4.4 bipyridine, hfipbb = 4,4 '- (hexafluororisopropylidene) -bisbenzoate, cyclam = 1, 4,8, 1 1 - tetraazacyclotetradecane, imz = imidazolates.
Figure imgf000003_0001
Figure imgf000003_0001
Par connecteur, on désigne l'entité inorganique dudit matériau hybride. Il peut s'agir d'un cation seul, d'un dimère, trimère ou tétramère ou encore d'une chaîne ou d'un plan. Les équipes de Yaghi et Férey ont ainsi décrit un nombre important de nouveaux matériaux hybrides (série des MOF - " Métal Organic Framework " - et série des MIL - " Matériaux de l'Institut Lavoisier " - respectivement). De nombreuses autres équipes ont suivi cette voie et aujourd'hui le nombre de nouveaux matériaux hybrides décrits est en pleine expansion. Le plus souvent, les études visent à mettre au point des structures ordonnées, présentant des volumes poreux extrêmement importants, une bonne stabilité thermique et des fonctionnalités chimiques ajustables. Connector means the inorganic entity of said hybrid material. It can be a single cation, a dimer, trimer or tetramer or a chain or a plane. The teams of Yaghi and Férey have thus described a large number of new hybrid materials (series of MOFs - "Metal Organic Framework" - and series of MIL - "Materials of the Lavoisier Institute" - respectively). Many other teams have followed this path and today the number of new hybrid materials described is expanding. Most often, the studies are aimed at developing ordered structures with extremely large pore volumes, good thermal stability, and adjustable chemical functionality.
Par exemple, Yaghi et al. décrivent une série de structures à base de bore dans la demande de brevet US 2006/0154807 et indiquent leur intérêt dans le domaine du stockage des gaz. Le brevet US 7,202.385 divulgue un récapitulatif particulièrement complet des structures décrites dans la littérature et illustre parfaitement la multitude de matériaux hybrides existants à ce jour.  For example, Yaghi et al. disclose a series of boron structures in US patent application 2006/0154807 and indicate their interest in the field of gas storage. US Pat. No. 7,202,385 discloses a particularly complete summary of the structures described in the literature and perfectly illustrates the multitude of hybrid materials existing to date.
La synthèse des matériaux hybrides organique-inorganique cristallisés (MHOIC) est particulièrement documentée à la fois dans la littérature brevet et dans la littérature ouverte. Or, ces poudres doivent être mises en forme afin d'envisager une utilisation dans des applications industrielles et dans ce domaine, peu de références sont disponibles comme indiqué par Tagliabue et al. The synthesis of crystalline organic-inorganic hybrid materials (MHOIC) is particularly well documented both in the patent literature and in the open literature. However, these powders must be shaped to consider use in industrial applications and in this area, few references are available as indicated by Tagliabue et al.
La mise en forme des matériaux hybrides organique-inorganique cristallisés (MHOIC) est généralement abordée par te biais du procédé de compaction : soit en compression directe (Tagliabue et al., Méthane storage on CPO-27 pellets, J. Porous Mater (201 1 ) 1 8, 289-296), soit en compression en ajoutant des polymères, ou une alumine ou des noirs de carbone (Cavenati et al., Metal organic framework adsorbent for biogas upgrading, Ind. Eng. Chem. Res. 2008, 47, 6333-6335).  The shaping of crystalline organic-inorganic hybrid materials (MHOIC) is generally approached through the compaction process: either in direct compression (Tagliabue et al., Methane storage on CPO-27 pellets, J. Porous Mater (201 1)). 18, 289-296), either in compression by adding polymers, or alumina or carbon blacks (Cavenati et al., Metal organic framework adsorbent for biogas upgrading, Ind Eng Eng Chem Res 2008, 47). 6333-6335).
Finsy et al. (Finsy et al., Séparation of CO2/CH4 mixtures vvith the MIL53(AI) metal-organic framework, Microporous and mesoporous matériels, 120 (2009) 221 -227) décrit la préparation de matériaux MIL-53 mis en forme par évaporation sous agitation du solvant dans lequel a été préalablement dissout le polymère (alcool polyvinylïque PVA, présent à hauteur de 13% poids par rapport à la masse totale du matériau) et ont étudié les propriétés de séparation sur colonne des agglomérats obtenus. Finsy et al. décrit la préparation d'objets de taille comprise entre 500 et 630 μm. Aucune précision sur les propriétés mécaniques des granules obtenues et en particulier sur la résistance à l'écrasement n'est fournie mais il est observé que la réduction du volume microporeux est de 32% après activation à 190ºC. Finsy et al. (Finsy et al., Separation of CO 2 / CH 4 mixtures vvith the MIL53 (AI) metal-organic framework, Microporous and mesoporous materials, 120 (2009) 221-227) describes the preparation of MIL-53 materials shaped by stirring evaporation of the solvent in which the polymer (polyvinyl alcohol PVA, present at a level of 13% by weight relative to the total mass of the material) was previously dissolved and studied the column separation properties of the agglomerates obtained. Finsy et al. describes the preparation of objects of size between 500 and 630 microns. No details on the mechanical properties of obtained granules and in particular on the crush resistance is provided but it is observed that the reduction of the microporous volume is 32% after activation at 190ºC.
La demande de brevet US2003/0222023A 1 (BASF) décrit des matériaux mis en forme de type MOF préparés par la mise en forme d'une composition comprenant un matériau hybride organique-inorganique cristallisé et un liant, Toutes ies techniques de mise en forme sont décrites : pastillage, malaxage, extrusion, granulation, etc.... Les matériaux décrits comme liants dans le texte sont des composés inorganiques, minéraux tels que la silice, l'alumine, l'argile ou le graphite et des composés organiques tels que les silanes. Des polymères hydrophiles comme le PVA (alcool polyvinylique) et la PVP (poiyvinylpyrrolidone) sont cités comme agent épaississant de la préparation avant la mise en forme. Les exemples de la demande US2003/0222023A 1 ne mentionnent que la mise en forme de tels matériaux par pastillage. Les matériaux obtenus possèdent une résistance à l'écrasement de 2 à 100 N. Patent Application US2003 / 0222023A1 (BASF) discloses shaped materials of the MOF type prepared by shaping a composition comprising a crystallized organic-inorganic hybrid material and a binder. All shaping techniques are described: pelletizing, kneading, extrusion, granulation, etc. The materials described as binders in the text are inorganic compounds, minerals such as silica, alumina, clay or graphite and organic compounds such as silanes. Hydrophilic polymers such as PVA (polyvinyl alcohol) and PVP (polyvinylpyrrolidone) are cited as a thickener of the preparation prior to shaping. The examples of the application US2003 / 0222023A 1 mention only the shaping of such materials by pelletizing. The materials obtained have a crush strength of 2 to 100 N.
Le brevet US7637983B 1 décrit des membranes comprenant une phase organique polymère continue et un matériau hybride organique-inorganique cristallisé dispersé dans la phase continue polymère, leur procédé de préparation et un procédé de séparation de gaz par mise en contact d'un gaz avec ladite membrane. Les membranes sont préparées par mélange d'une solution de polymère avec une poudre de matériau hybride organique-inorganique cristallisé pour former une dispersion et le mélange est ensuite coulé pour former une membrane. Les exemples du brevet US7637983 mentionnent des membranes contenant 20 à 30% de matériau hybride organique-inorganique cristallisé avec une matrice polyimide (Matrimid, Ultem). US Pat. No. 3,737,983B1 discloses membranes comprising a continuous polymer organic phase and a crystallized organic-inorganic hybrid material dispersed in the continuous polymer phase, their method of preparation and a process for separating gas by bringing a gas into contact with said membrane . The membranes are prepared by mixing a polymer solution with a crystalline organic-inorganic hybrid material powder to form a dispersion and the mixture is then cast to form a membrane. The examples of US Pat. No. 3,737,983 mention membranes containing 20 to 30% of hybrid organic-inorganic material crystallized with a polyimide matrix (Matrimid, Ultem).
La demande de brevet WO 201 1/100501 A 1 (Dow Global Technologies) décrit également des membranes composites destinées à la séparation des gaz. La membrane est constituée d'une phase organo-métallique et d'une phase polymérique. Les polymères auto associatifs (organisation par des liaisons non covaientes : liaison hydrogène, ioniques, intermoléculaires) sont décrits. Les compositions contiennent de 1 à 70% poids de matériau hybride organique- inorganique cristallisé. Le chapitre 15 du livre "Metal-Organic Frameworks : Applications from Catalysis to Gas Storage" publié chez Wiley reprend les techniques de mise en forme de matériau hybride organique-inorganique cristallisé suivant les applications visées. Sont décrites les différentes techniques de dépôt sur fibre, et les procédés sol-gels permettant de réaliser des monolithes d'aérogels notamment, dans ce cas, certains agents liants comme le PET et les silicones par exemple sont utilisés. Sont également décrites les mises en forme par extrusion pour obtenir des monolithes de tailles d'environ 200 mm, dans ce cas, le polymère méthyîcellulose est cité comme agent plastifiant. The patent application WO 201 1/100501 A1 (Dow Global Technologies) also describes composite membranes intended for the separation of gases. The membrane consists of an organometallic phase and a polymeric phase. The self associative polymers (organization by non-covenant bonds: hydrogen bond, ionic, intermolecular) are described. The compositions contain from 1 to 70% by weight of crystallized organic-inorganic hybrid material. Chapter 15 of the book "Metal-Organic Frameworks: Applications from Catalysis to Gas Storage" published by Wiley takes the techniques of shaping hybrid organic-inorganic material crystallized according to the intended applications. Are described the different fiber deposition techniques, and sol-gel processes for producing aerogels monoliths, in this case, certain binding agents such as PET and silicones, for example, are used. Also described are extrusion shaping to obtain monoliths of sizes of about 200 mm, in which case the methylcellulose polymer is cited as a plasticizer.
Toutefois, ces types de mise en forme (membranes, granulés, monolithes) sont inadaptées à des utilisations en réacteurs à lit fixe ou mobile fréquemment usités dans le domaine de la catalyse, de la séparation ou du stockage de gaz. Les extrudés ou billes millimétriques sont les formes les plus répandues et utilisées pour ces applications. Dans le cas de la compression directe sans liant, les forces de capillarité et la pénétration des solvants peuvent entraîner la destruction du matériau et une génération de fines aux conséquences désastreuses pour le procédé. En outre, la diminution du volume microporeux (en lien avec une amorphisation/destruction partielle du matériau par la compression ou par bouchage de la porosité par les liants) est souvent mentionnée et peut constituer un obstacle au maintien de performances catalytïques ou séparatrices des MOF.  However, these types of shaping (membranes, granules, monoliths) are unsuitable for uses in fixed bed or mobile bed reactors frequently used in the field of catalysis, separation or storage of gas. Extrusions or millimeter balls are the most common forms used for these applications. In the case of direct compression without binder, the capillary forces and the penetration of the solvents can lead to the destruction of the material and a generation of fines with disastrous consequences for the process. In addition, the decrease in the microporous volume (in connection with amorphization / partial destruction of the material by compression or by blocking of the porosity by the binders) is often mentioned and may be an obstacle to maintaining catalytic or separating performances of the MOFs.
De manière surprenante, la demanderesse a mis en évidence que les interactions polymères- matériau hybride organique-inorganique cristallisé étaient suffisamment fortes pour maintenir la cohésion de composites polymères-matériau hybride organique-inorganique cristallisé sous forme d'extrudés, alors que certains composés organiques comme les polymères sont usuellement utilisés comme agents épaississants dans l'art antérieur. Il apparaît notamment que la polyvinylpyrrolidone ou certains polyimides sont particulièrement adaptés à la mise en forme de matériau hybride organique-inorganique cristallisé. Un objectif de la présente invention est de fournir un nouveau matériau composite comprenant au moins un matériau hybride organique-inorganique cristallisé mis en forme sous forme d'extrudé avec une formulation liante comprenant au moins un liant polymère, ledit matériau présentant une teneur élevée en un matériau hybride organique-inorganique cristallisé, Surprisingly, the Applicant has demonstrated that the polymer-organic hybrid-inorganic crystallized material interactions were strong enough to maintain the cohesion of polymer composites-organic-inorganic hybrid material crystallized in the form of extrudates, whereas certain organic compounds such as the polymers are usually used as thickeners in the prior art. It appears in particular that polyvinylpyrrolidone or certain polyimides are particularly suitable for shaping crystallized organic-inorganic hybrid material. An object of the present invention is to provide a new composite material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material having a high content of one crystallized organic-inorganic hybrid material,
Un autre objectif de la présente invention est de fournir un nouveau procédé de préparation dudit matériau comprenant au moins un matériau hybride organique-inorganique cristallisé (MHOIC) mis en forme sous forme d'extrudés avec une formulation liante comprenant au moins un polymère. Another object of the present invention is to provide a new process for preparing said material comprising at least one crystallized organic-inorganic hybrid material (MHOIC) shaped as extrudates with a binder formulation comprising at least one polymer.
Résumé de l'invention : Summary of the invention
En particulier, la présente invention concerne un matériau comprenant au moins un matériau hybride organique-inorganique cristallisé mis en forme sous forme d'extrudé avec une formulation liante comprenant au moins un liant polymère, ledit matériau étant constitué de 80 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 20% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau. In particular, the present invention relates to a material comprising at least one crystallized organic-inorganic hybrid material shaped in the form of an extrusion with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystalline organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
La présente invention concerne également un procédé de préparation dudit matériau comprenant au moins les étapes suivantes : The present invention also relates to a process for preparing said material comprising at least the following steps:
a) une étape de mélange d'au moins 80 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC) avec au moins 1 à 20% poids d'une poudre d'au moins un polymère et un solvant pour obtenir un mélange, les pourcentages poids étant exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a), b) une étape de mise en forme par extrusion du mélange obtenu à l'issue de l'étape a), c) une étape de traitement thermique du matériau mis en forme obtenu à l'issue de l'étape b), ladite étape de traitement thermique étant réalisée à une température comprise entre 25 eta) a step of mixing at least 80 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) with at least 1 to 20% by weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a), b) a step of shaping by extrusion of the mixture obtained at the end of the step a), c) a heat treatment step of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and
300°C, pendant une durée comprise entre 1 minute et 72 heures. 300 ° C, for a period of between 1 minute and 72 hours.
Un avantage de la présente invention est de fournir un matériau et son procédé de préparation permettant sa mise en forme avec une teneur en matériau hybride organique-inorganique cristallisé élevée et en particulier comprise entre 80 et 99% poids par rapport à la masse du matériau, ledit matériau obtenu présentant à la fois une bonne résistance mécanique et une perte de volume microporeux par rapport à la porosité du matériau hybride organique- inorganique cristallisé de départ limitée. Le matériau ainsi obtenu est adapté à une utilisation dans un procédé industriel sur de longues périodes. Description détaillée An advantage of the present invention is to provide a material and its preparation process allowing its shaping with a content of high crystallized organic-inorganic hybrid material and in particular between 80 and 99% by weight relative to the mass of the material, said obtained material having both a good mechanical strength and a loss of microporous volume with respect to the porosity of the starting crystallized organic-inorganic hybrid material limited. The material thus obtained is suitable for use in an industrial process over long periods. detailed description
Le matériau selon la présente invention comprend au moins un matériau hybride organique- inorganique cristallisé mis en forme sous forme d'extrudé avec une formulation liante comprenant au moins un liant polymère, ledit matériau étant constitué de 80 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 20% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau.  The material according to the present invention comprises at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
Le(s)dït(s) matériau(x) hybride(s) organique-inorganique cristallisé(s) utilisé(s) (MHOIC) dans le matériau selon la présente invention sont de préférence choisis parmi les MOF (Métal Organic Framework selon la terminologie anglo-saxonne), les ZlFs (ou Zeolitic Imidazolate Frameworks selon la terminologie anglo-saxonne), les MILs (ou Matériaux de l'Institut Lavoisier), les IRMOFs (ou isoReticular Métal Organic Framework selon la terminologie anglo-saxonne), seuls ou en mélange. The crystalline organic-inorganic hybrid material (s) used (MHOIC) used in the material according to the present invention are preferably selected from the MOF (Metal Organic Framework according to US Pat. English terminology), the ZlFs (or Zeolitic Imidazolate Frameworks according to the English terminology), the MILs (or Materials of the Lavoisier Institute), the IRMOFs (or isoReticular Metal Organic Framework according to the English terminology), only or in mixture.
De manière préférée, le(s)dit(s) matériau(x) hybride(s) organique-inorganique cristallisé(s) utilisé(s) (MHOIC) dans le matériau selon la présente invention sont choisis parmi la liste suivante : SIM-1 , HKUST, CAU-1 , MOF-5, MOF-38, MOF-305, MOF-37, MOF- 12, IRMOF-2 à - 16, MIL-53, MIL-68, MIL- 101 , ZIF-8, ZIF- 1 1 , ZIF-67, ZIF-90, seuls ou en mélange. Preferably, said crystalline organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from the following list: 1, HKUST, CAU-1, MOF-5, MOF-38, MOF-305, MOF-37, MOF-12, IRMOF-2 to -16, MIL-53, MIL-68, MIL-101, ZIF-8 , ZIF-1 1, ZIF-67, ZIF-90, alone or in admixture.
De manière très préférée, le(s)dit(s) matériau(x) hybride(s) organique-inorganique cristallisé(s) utilisé(s) (MHOIC) dans le matériau selon la présente invention sont choisis parmi le SIM- 1 , le HKUST et le ZIF-8, seuls ou en mélange. Very preferably, the said hybridized organic-inorganic hybrid material (s) used (MHOIC) in the material according to the present invention are chosen from SIM-1, HKUST and ZIF-8, alone or mixed.
Le(s)dit(s) matériau(x) hybride(s) organique-inorganique cristallisé(s) (MHOIC) sont utilisés dans l'étape a) du procédé de préparation selon l'invention sous forme de poudre.  The said crystallized organic-inorganic hybrid material (s) (MHOIC) are used in step a) of the preparation process according to the invention in powder form.
Le(s)dit(s) liant(s) polymère(s) est (sont) avantageusement choisi(s) parmi les polymères bien connus de l'Homme du métier. De manière préférée, le(s)dit(s) polymère(s) est (sont) choisi(s) parmi les polyvinylpyrrolidones, les polymères cellulosiques et leurs dérivés, de préférence choisis parmi les éthers de cellulose tels que par exemple le Methocel, commercialisé par la société Dow Chemical, les alcools polyvinyliques, les polyéthylènes glycols, les poiyacrylamides, les polysaccharides, les polymères naturels et leurs dérivés tels que par exemple les alginates, les polyesters, les polyamides et polyamides aromatiques, les polyéthers les poly (aryéther), les polyuréthanes, les polysulfones tels que les polyéthers sulfones, les polymères hétérocyliques, de préférence choisis parmi les polyimides, les polyéthers imides, les polyesters imides, les polyamides imides, et les polybenzimidazoles. De préférence, le(s)dit(s) liant(s) polymère(s) est (sont) choisi(s) parmi les polyvinylpyrrolidones, les polymères hétérocycliques et les polymères cellulosiques et de manière très préférée, parmi les polyvinylpyrrolidones, les polyimides et les éthers de cellulose. The said (s) binder (s) polymer (s) is (are) advantageously chosen (s) among the polymers well known to those skilled in the art. Preferably, the said polymer (s) is (are) chosen from polyvinylpyrrolidones, cellulosic polymers and their derivatives, preferably chosen from cellulose ethers such as, for example, Methocel, sold by Dow Chemical, polyvinyl alcohols, polyethylene glycols, polyacrylamides, polysaccharides, natural polymers and their derivatives such as, for example, alginates, polyesters, polyamides and aromatic polyamides, polyethers poly (aryether), polyurethanes, polysulfones such as polyether sulfones, heterocylic polymers, preferably selected from polyimides, polyether imides, polyesters imides, polyamide imides, and polybenzimidazoles. Preferably, the said binder (s) polymer (s) is (are) chosen from polyvinylpyrrolidones, heterocyclic polymers and cellulosic polymers and very preferably from polyvinylpyrrolidones, polyimides and cellulose ethers.
On entend par polymère un composé présentant au moins 20 unités de répétition ou une masse moléculaire supérieure à 500 g.mol-1. By polymer is meant a compound having at least 20 repeating units or a molecular weight greater than 500 g.mol -1 .
De préférence, ledit matériau est constitué de 85 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 15% poids d'au moins un liant polymère, et de manière préférée de 90 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 10% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau. Preferably, said material consists of 85 to 99% by weight of at least one crystallized organic-inorganic hybrid material and 1 to 15% by weight of at least one polymeric binder, and preferably from 90 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 10% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
Conformément à l'invention, ledit matériau est sous forme d'extrudés. De préférence, ledit matériau est sous forme d'extrudés de diamètre compris entre 0,8 et 5 mm et de manière préférée entre 0,9 et 4 mm. According to the invention, said material is in the form of extrudates. Preferably, said material is in the form of extrudates with a diameter of between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
Lesdits matériaux selon l'invention ayant une teneur en matériau hybride organique- inorganique cristallisé (MHOIC) élevée, présentent des propriétés mécaniques accrues, notamment en terme de résistance mécanique, quelle que soit la teneur mise en œuvre, et sont résistants à une élévation de température modérée, ce qui permet d'envisager la mise en œuvre dudit matériau dans des procédés à des températures relativement élevées mais tout de même limitées par la tenue en température du matériau hybride organique-inorganique cristallisé (MHOIC) et/ou du polymère considéré. Said materials according to the invention having a high content of crystallized organic-inorganic hybrid material (MHOIC), have increased mechanical properties, especially in terms of mechanical strength, regardless of the content used, and are resistant to a rise in moderate temperature, which allows to consider the implementation of said material in processes at relatively high temperatures but still limited by the temperature resistance of the hybrid organic-inorganic crystalline material (MHOIC) and / or the polymer.
Lesdits matériaux selon l'invention peuvent donc être employés pour des applications en catalyse et séparation.  Said materials according to the invention can therefore be used for applications in catalysis and separation.
En particulier, lesdits matériaux selon l'invention présentent une résistance mécanique mesurée par le test d'écrasement grain à grain, notée par la suite EGG au moins supérieure à 0,4 daN/mm et de préférence au moins supérieure à 0,9 daN/mm et de manière préférée au moins supérieure à 1 daN/mm. In particular, said materials according to the invention have a mechanical resistance measured by the grain-to-grain crushing test, noted by EGG at least greater than 0.4 daN / mm and preferably at least greater than 0.9 daN / mm and preferably at least greater than 1 daN / mm.
On entend par résistance mécanique à l'écrasement latéral, la résistance mécanique du matériau selon l'invention déterminée par le test d'écrasement grain à grain (EGG). Il s'agit d'un test normalisé (norme ASTM D4179-01 ) qui consiste à soumettre un matériau sous forme d'objet millimétrique, comme une bille, une pastille ou un extrudé, à une force de compression générant la rupture. Ce test est donc une mesure de la résistance en traction du matériau. L'analyse est répétée sur un certain nombre de solides pris individuellement et typiquement sur un nombre de solides compris entre 10 et 200, La moyenne des forces latérales de rupture mesurées constitue l'EGG moyen qui est exprimé dans le cas des granules en unité de force (N), et dans le cas des extrudés en unité de force par unité de longueur (daN/mm ou décaNewton par millimètre de longueur d'extrudé).  By mechanical resistance to lateral crushing, the mechanical strength of the material according to the invention determined by the grain-to-grain (GGE) crushing test. This is a standardized test (ASTM D4179-01) that involves subjecting a material as a millimeter object, such as a ball, pellet, or extrusion, to a compressive force that causes the breakage. This test is therefore a measure of the tensile strength of the material. The analysis is repeated on a number of solids taken individually and typically on a number of solids between 10 and 200. The average of the lateral forces of rupture measured constitutes the average EGG which is expressed in the case of the granules in unit of force (N), and in the case of extrusions in unit of force per unit length (daN / mm or decaNewton per millimeter of extruded length).
Par ailleurs, en prenant en compte l'effet de dilution due à la présence du liant polymère dans les matériaux obtenus sous forme d'extrudé selon l'invention, lesdits matériaux selon l'invention présentent une perte de volume microporeux inférieure à 35%, de préférence inférieur à 30 %, de manière préférée inférieure à 25 et de manière plus préférée inférieure à 15%. Moreover, taking into account the effect of dilution due to the presence of the polymeric binder in the materials obtained in extruded form according to the invention, said materials according to the invention exhibit a loss of microporous volume of less than 35%, preferably less than 30%, preferably less than 25 and more preferably less than 15%.
La perte de micro porosité est calculée en tenant compte de la dilution due à la présence de liant polymère dans le matériau final sous forme d'extrudé : le volume microporeux du matériau obtenu sous forme d'extrudé est comparé à celui de la poudre de MHOIC de départ, pondéré du facteur de dilution qui est égal au pourcentage massique de MHOIC présent dans la matériau obtenu sous forme d'extrudé.  The loss of micro porosity is calculated taking into account the dilution due to the presence of polymer binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder. starting point, weighted with the dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in extruded form.
Pour ie matériau obtenu sous forme d'extrudé, la perte de microporosité = [(volume microporeux du MHOIC de départ x % massique de MHOIC présent dans le matériau final obtenu sous forme d'extrudé)/ 100 - volume microporeux du matériau final obtenu sous forme d'extrudé] x 100 / (volume microporeux du MHOIC de départ x % massique de MHOIC présent dans le matériau final obtenu sous forme d'extrudé)/100), La présente invention concerne également un procédé de préparation dudit matériau selon l'invention, le procédé de préparation du matériau comprenant au moins les étapes suivantes : a) une étape de mélange d'au moins 80 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC) avec au moins 1 à 20% poids d'une poudre d'au moins un polymère et un solvant pour obtenir un mélange, ies pourcentages poids étant exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a), b) une étape de mise en forme par extrusion du mélange obtenu à l'issue de l'étape a), c) une étape de traitement thermique du matériau mis en forme obtenu à l'issue de l'étape b), ladite étape de traitement thermique étant réalisée à une température comprise entre 25 et 300°C, pendant une durée comprise entre 1 minute et 72 heures. For the material obtained in extruded form, the loss of microporosity = [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x% by mass of MHOIC present in the final material obtained in extruded form) / 100). The present invention also relates to a process for the preparation of said material according to the invention. invention, the method of preparing the material comprising at least the following steps: a) a step of mixing at least 80 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) with at least 1 to 20% by weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a), b) a step of extrusion shaping of the mixture obtained at the end of step a), c) a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C., for a period of time between 1 minute and 72 hours.
La somme des quantités de chacune des poudres introduites dans ladite étape a) est égale à 100%.  The sum of the amounts of each of the powders introduced in said step a) is equal to 100%.
Étape a) : Step a):
Conformément à l'invention, ladite étape a) consiste en le mélange d'au moins 80 à 99% poids et de préférence d'au moins 85 à 99% poids et de manière préféré d'au moins 90 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC), avec au moins 1 à 20% poids et de préférence avec au moins 1 à 15% poids et de manière préféré d'au moins 1 à 10% poids d'une poudre d'au moins un polymère et un solvant pour obtenir un mélange. Le(s)dit(s) matériau(x) hybride(s) organique-inorganique cristallisé(s) (MHOIC) utilisé(s) sous forme de poudre dans le procédé de préparation du matériau selon la présente invention et les polymères sont décrits plus haut.  According to the invention, said step a) consists of mixing at least 80 to 99% by weight and preferably at least 85 to 99% by weight and preferably at least 90 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC), with at least 1 to 20% by weight and preferably with at least 1 to 15% by weight and more preferably at least 1 to 10% by weight of a powder of at least one polymer and a solvent to obtain a mixture. The said crystallized organic-inorganic hybrid material (s) (MHOIC) used in powder form in the process for preparing the material according to the present invention and the polymers are described. upper.
Ledit solvant est avantageusement choisi parmi l'eau, les alcools de préférence choisis parmi l'éthanol et le méthanol, les aminés, les éthers, les esters, les cétones, les lactones, les phénols, les crésols, les solvants aprotiques polaires comme le DMF, le DMAC, la NMP par exemple. Said solvent is advantageously chosen from water, the alcohols preferably chosen from ethanol and methanol, amines, ethers, esters, ketones, lactones, phenols, cresols, polar aprotic solvents such as DMF, DMAC, NMP for example.
Dans le cadre de l'invention, il est tout à fait envisageable de procéder à des mélanges de plusieurs poudres de matériaux hybrides organique-inorganique cristallisés (MHOIC) différents et/ou de polymères et/ou de solvants. In the context of the invention, it is quite possible to carry out mixtures of several powders of different crystalline organic-inorganic hybrid materials (MHOIC) and / or polymers and / or solvents.
Le ou les polymères peuvent être mélangés sous forme de poudre ou en solution dans ledit solvant. Pour des raisons de mise en œuvre, on pourra appliquer une température afin de favoriser le gonflement ou la solubilisation du polymère ou encore régler la viscosité de l'ensemble. The polymer (s) may be mixed in powder form or in solution in said solvent. For reasons of implementation, we can apply a temperature in order to promote the swelling or solubilization of the polymer or adjust the viscosity of the assembly.
L'ordre dans lequel le mélange des poudres d'au moins un matériau hybride organique- inorganique cristallisé (MHOIC), d'au moins un polymère et du solvant est réalisé est indifférent. The order in which the mixture of the powders of at least one crystalline organic-inorganic hybrid material (MHOIC), at least one polymer and the solvent is produced is indifferent.
Le mélange desdites poudres et dudit solvant peut avantageusement être réalisé en une seule fois.  The mixture of said powders and of said solvent can advantageously be produced at one time.
Les ajouts de poudres et de solvant peuvent également avantageusement être alternés.  Additions of powders and solvent can also advantageously be alternated.
Dans un mode de réalisation préféré, lesdites poudres d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC), d'au moins un polymère, dans le cas ou ceux-ci sont mélangés sous forme de poudres, sont d'abord pré-mélangées, à sec, avant l'introduction du solvant. In a preferred embodiment, said powders of at least one crystalline organic-inorganic hybrid material (MHOIC), of at least one polymer, in the case where they are mixed in the form of powders, are firstly prepared. -mixed, dry, before the introduction of the solvent.
Lesdites poudres pré-mélangées sont ensuite avantageusement mises en contact avec ledit solvant. Dans un autre mode de réalisation, les polymères peuvent préalablement être en solution ou suspension dans ledit solvant quand ledit solvant est mis en contact avec les poudres d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC). La mise en contact avec ledit solvant conduit à l'obtention d'un mélange qui est ensuite malaxé. Said premixed powders are then advantageously brought into contact with said solvent. In another embodiment, the polymers may previously be in solution or suspension in said solvent when said solvent is brought into contact with the powders of at least one crystalline organic-inorganic hybrid material (MHOIC). Contacting with said solvent leads to obtaining a mixture which is then kneaded.
De préférence, ladite étape a) de mélange est réalisée par malaxage, en batch ou en continu. Dans le cas où ladite étape a) est réalisée en batch, ladite étape a) est avantageusement réalisée dans un malaxeur de préférence équipé de bras en Z, ou à cames, ou dans tout autre type de mélangeur tel que par exemple un mélangeur planétaire, Ladite étape a) de mélange permet d'obtenir un mélange homogène des constituants pulvérulents et du solvant, Preferably, said mixing step a) is carried out by mixing, batchwise or continuously. In the case where said step a) is carried out in batch, said step a) is advantageously carried out in a kneader preferably equipped with Z-arms, or with cams, or in any other type of mixer such as for example a planetary mixer, Said step a) of mixing makes it possible to obtain a homogeneous mixture of powder constituents and of the solvent,
De préférence, ladite étape a) est mise en œuvre pendant une durée comprise entre 5 et 60 min, et de préférence entre 10 et 50 min, La vitesse de rotation des bras du malaxeur est avantageusement comprise entre 10 et 75 tours/minute, de façon préférée entre 25 et 50 tours/minute. Étape b) ; Preferably, said step a) is carried out for a period of between 5 and 60 minutes, and preferably between 10 and 50 minutes. The rotation speed of the kneader arms is advantageously between 10 and 75 revolutions / minute. preferred way between 25 and 50 rpm. Step b);
Conformément à l'invention, ladite étape b) consiste en ia mise en forme par extrusion du mélange obtenu à l'issue de l'étape a) de mélange. Ladite étape b) est avantageusement réalisée dans une extrudeuse piston, mono-vis ou bi-vis. Dans ce cas, un adjuvant organique peut éventuellement être ajouté dans l'étape a) de mélange. La présence dudit adjuvant organique facilite la mise en forme par extrusion.  According to the invention, said step b) consists in shaping by extrusion of the mixture obtained at the end of step a) of mixing. Said step b) is advantageously carried out in a piston, single-screw or twin-screw extruder. In this case, an organic adjuvant may optionally be added in the mixing step a). The presence of said organic adjuvant facilitates extrusion shaping.
Dans le cas où ledit procédé de préparation est mis en œuvre en continu, ladite étape a) de mélange peut être couplée avec l'étape b) de mise en forme par extrusion dans un même équipement. Selon cette mise en œuvre, i'extrusîon du mélange nommé aussi "pâte malaxée" peut être réalisée soit en extrudant directement en bout de malaxeur continu de type bi-vis par exemple, soit en reliant un ou plusieurs malaxeurs batch à une extrudeuse. La géométrie de la filière, qui confère leur forme aux extrudés, peut être choisie parmi les filières bien connues de l'Homme du métier. Elles peuvent ainsi être par exemple, de forme cylindrique, multilobée, cannelée ou à fentes. In the case where said preparation process is carried out continuously, said mixing step a) can be coupled with the extrusion shaping step b) in the same equipment. According to this embodiment, the extrusion of the mixture also called "kneaded paste" can be carried out either by directly extruding the end of continuous twin-screw kneader for example, or by connecting one or more batch kneaders to an extruder. The geometry of the die, which confers their shape to the extrudates, can be chosen from the well-known dies of the skilled person. They can thus be, for example, cylindrical, multilobed, fluted or slotted.
Dans ie cas où la mise en forme du mélange issu de l'étape a) est réalisée par extrusion, la quantité de solvant ajoutée dans l'étape a) de mélange est ajustée de façon à obtenir, à l'issue de cette étape et quelle que soit la variante mise en œuvre, un mélange ou une pâte qui ne coule pas mais qui n'est pas non plus trop sèche afin de permettre son extrusion dans des conditions convenables de pression et de température bien connues de l'Homme du métier et dépendantes de l'équipement d'extrusion utilisé. In the case where the shaping of the mixture resulting from step a) is carried out by extrusion, the amount of solvent added in step a) of mixing is adjusted so as to obtain, at the end of this step and whatever the variant used, a mixture or a paste that does not flow but is not too dry to allow its extrusion under suitable conditions of pressure and temperature well known to those skilled in the art and dependent on the extrusion equipment used.
De préférence, ladite étape b) de mise en forme par extrusion est opérée à une pression d'extrusion supérieure à 1 MPa et de préférence comprise entre 3 MPa et 10 MPa.  Preferably, said extrusion forming step b) is carried out at an extrusion pressure greater than 1 MPa and preferably between 3 MPa and 10 MPa.
Étape c) : Step c):
Conformément à l'invention, ladite étape c) consiste en une étape de traitement thermique du matériau mis en forme obtenu à l'issue de l'étape b), ladite étape de traitement thermique étant réalisée à une température comprise entre 25 et 300°C, de préférence comprise entre 25 et 200°C et de manière préférée comprise entre 25 et 150°C, pendant une durée comprise entre 1 minute et 72 heures, de préférence entre 30 minutes et 72 h, et de manière préférée entre 1 h et 48 h et de manière plus préférée entre 1 et 12 h. Ladite étape de traitement thermique est de préférence une étape de maturation et peut avantageusement être effectuée sous gaz inerte ou sous vide. De préférence, ladite étape de maturation est effectuée sous air. A l'issue du procédé de préparation du matériau selon l'invention, le matériau obtenu se présente sous forme d'extrudés de taille comprise entre 0,8 et 5 mm et de préférence entre 0,9 et 4 mm. According to the invention, said step c) consists of a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C, preferably between 25 and 200 ° C and preferably between 25 and 150 ° C for a period of between 1 minute and 72 hours, preferably between 30 minutes and 72 hours, and preferably between 1 hour and 48 h and more preferably between 1 and 12 h. Said heat treatment step is preferably a maturation step and can advantageously be carried out under inert gas or under vacuum. Preferably, said maturation step is carried out under air. At the end of the process for preparing the material according to the invention, the material obtained is in the form of extrudates of size between 0.8 and 5 mm and preferably between 0.9 and 4 mm.
Cependant, il n'est pas exclu que lesdits matériaux obtenus soient ensuite, par exemple, introduits dans un équipement permettant d'arrondir leur surface, tel qu'un drageoir ou tout autre équipement permettant leur sphéronisation. However, it is not excluded that said materials obtained are then, for example, introduced into equipment for rounding their surface, such as a bezel or other equipment allowing their spheronization.
Ledit procédé de préparation selon l'invention permet d'obtenir des matériaux selon l'invention présentant des valeurs de résistance mécanique mesurées par écrasement grain à grain supérieures à 0,4 daN/mm, de préférence supérieure à 0,9 daN/mm et de manière préférée supérieure à 1 daN/mm, quelle que soit la teneur en (MHOIC) mise en œuvre. Said method of preparation according to the invention makes it possible to obtain materials according to the invention having mechanical strength values measured by grain-to-grain crushing greater than 0.4 daN / mm, preferably greater than 0.9 daN / mm and preferably greater than 1 daN / mm, regardless of the content of (MHOIC) implemented.
Le matériau obtenu à l'issue du procédé de préparation selon l'invention peut être utilisé pour des applications en catalyse, séparation, purification, captage... The material obtained at the end of the preparation process according to the invention can be used for applications in catalysis, separation, purification, capture ...
Ledit matériau est mis en contact avec la charge gazeuse à traiter dans un réacteur, qui peut être soit un réacteur en lit fixe, soit un réacteur radial, ou bien encore un réacteur en lit fluidisé. Said material is brought into contact with the gaseous feedstock to be treated in a reactor, which can be either a fixed bed reactor, a radial reactor, or a fluidized bed reactor.
Dans le cas d'une application dans les domaines de la catalyse et des séparations, la valeur d'EGG attendue est supérieure à 0,9 daN.mm- 1 , de préférence supérieure à 1 ,0 daN.mm- 1. In the case of an application in the fields of catalysis and separations, the expected EGG value is greater than 0.9 daN.mm -1 , preferably greater than 1.0 daN.mm -1 .
Les exemples ci- dessous illustrent l'invention sans en limiter la portée, EXEMPLES The examples below illustrate the invention without limiting its scope. EXAMPLES
Afin d'exemplifier l'invention, plusieurs mode de préparation sont décrits, sur la base de la mise en forme d'un matériau hybride organique-inorganique cristallisé MHOIC en particulier le ZTF-8, disponible commercialement sous l'appellation Basolite Z1200 (Sigma Aldrich). Les caractéristiques des matières premières sont récapitulées dans le tableau 1 : In order to exemplify the invention, several methods of preparation are described, on the basis of the shaping of a hybrid organic-inorganic hybrid material MHOIC, in particular ZTF-8, commercially available under the name Basolite Z1200 (Sigma Aldrich). The characteristics of the raw materials are summarized in Table 1:
Figure imgf000015_0001
Figure imgf000015_0001
Exemple 1 : Example 1
Etape a)  Step a)
Dans un réacteur en verre équipé d'une agitation mécanique, on introduit 4 g d'une poudre de polymère polyimide Matrimid 5218 commercialisé par Hunstman Advanced Materials (représentant 9% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) et 36 g de DMAC (diméthylacétamide). On porte à 70°C jusqu'à solubilîsation complète du polymère, on refroidit la solution et on additionne 40 g d'une poudre de ZIF-8 (Basoiite Z 1200) (représentant 91 % poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)). On poursuit ensuite l'agitation jusqu'à l'obtention d'une suspension assimilée à une pâte visqueuse. 4 g of a Matrimid 5218 polyimide polymer powder marketed by Hunstman Advanced Materials (representing 9% by weight relative to the total amount of powders introduced in said step a) are introduced into a glass reactor equipped with mechanical stirring. and 36 g of DMAC (dimethylacetamide). The mixture is heated to 70 ° C. until the polymer has dissolved completely, the solution is cooled and 40 g of a ZIF-8 powder (Basoiite Z 1200) (representing 91% by weight relative to the total amount of powders) are added. introduced in said step a)). Stirring is then continued until a suspension assimilated to a viscous paste is obtained.
Étape b)  Step b)
On introduit la pâte visqueuse dans une extrudeuse à main (filière de diamètre 3 mm) et on applique une pression suffisante afin d'obtenir un jonc qui est découpé en extrudés de 1 cm de longueur.  The viscous paste is introduced into a hand extruder (3 mm diameter die) and a sufficient pressure is applied to obtain a rod which is cut into extrudates of 1 cm in length.
Étape c)  Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 5 heures à 140°C sous le vide d'une pompe à palettes,  In order to eliminate the solvent, the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
Exemple 2 : Example 2
Étape a)  Step a)
Dans un réacteur en verre équipé d'une agitation mécanique, on introduit sous agitation 4 g d'une poudre de polymère polyimide Matrïmid 5218 commercialisé par Hunstman Advanced Materials (représentant 9% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) et 40 g d'une poude de ZIF-8 (Basolite Z1200))(représentant 91 % poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)). Lorsque le mélange de poudre paraît homogène, on additionne par petites fractions 36 g de DMAC (diméthylacétamide) puis on porte à 70°C l'ensemble sous agitation jusqu'à l'obtention d'une suspension assimilée à une pâte visqueuse après refroidissement. 4 g of a Matrimid 5218 polyimide polymer powder marketed by Hunstman Advanced are introduced with stirring into a glass reactor equipped with mechanical stirring. Materials (representing 9% by weight relative to the total amount of powders introduced in said step a)) and 40 g of a ZIF-8 pouch (Basolite Z1200) (representing 91% by weight expressed in relation to the total amount). of powders introduced in said step a)). When the powder mixture appears to be homogeneous, 36 g of DMAC (dimethylacetamide) are added in small portions, and then the mixture is brought to 70 ° C. with stirring until a suspension equivalent to a viscous paste is obtained after cooling.
Étape b) Step b)
On introduit la pâte visqueuse dans une extrudeuse à main (filière ø 3 mm) et on applique une pression suffisante afin d'obtenir un jonc qui est découpé en extrudés de 1 cm de longueur. Étape c)  The viscous paste is introduced into a hand extruder (die ø 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length. Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 5 heures à 140°C sous le vide d'une pompe à palettes.  In order to remove the solvent, the extrudates are subjected to a heat treatment of 5 hours at 140 ° C. under a vacuum of a vane pump.
Exemple 3 Example 3
Étape a) Step a)
Dans un réacteur en verre équipé d'une agitation mécanique, on introduit 0,36 g d'une poudre de polyvinylpyrrolidone (PVP) commercialisée par Aldrich (représentant 8,25% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) et 3,64 g de méthanol. On agite jusqu'à solubilisation complète du polymère et on additionne 4 g d'une poudre de ZIF-8 (Basolite Z1200)(représentant 91 ,75% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)). On poursuit ensuite l'agitation jusqu'à l'obtention d'une suspension assimilée à une pâte visqueuse.  0.36 g of a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 8.25% by weight expressed relative to the total amount of powders introduced into said stage are introduced into a glass reactor equipped with mechanical stirring. a)) and 3.64 g of methanol. The mixture is stirred until complete solubilization of the polymer and 4 g of a ZIF-8 powder (Basolite Z1200) (representing 91.75% by weight relative to the total amount of powders introduced in said step a) are added. Stirring is then continued until a suspension assimilated to a viscous paste is obtained.
Étape b) Step b)
On introduit la pâte visqueuse dans une extrudeuse à main (filière ø 3 mm) et on applique une pression suffisante afin d'obtenir un jonc qui est découpé en extrudés de 1 cm de longueur. Étape c)  The viscous paste is introduced into a hand extruder (die ø 3 mm) and sufficient pressure is applied to obtain a rod which is cut into extruded 1 cm in length. Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 3 heures à 80°C sous le vide d'une pompe à palettes. Exemple 4 :  In order to eliminate the solvent, the extrudates are subjected to a heat treatment of 3 hours at 80 ° C. under a vacuum of a vane pump. Example 4
Étape a) Dans un réacteur en verre équipé d'une agitation mécanique, on introduit 2, 1 g d'une poudre de polyvinylpyrrolidone (PVP) commercialisé par Aldrich (représentant 10% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) et 19 ml d'eau. On agite jusqu'à solubilisation complète du polymère. Step a) 2 g of a polyvinylpyrrolidone (PVP) powder marketed by Aldrich (representing 10% by weight relative to the total amount of powders introduced in said step a) are introduced into a glass reactor equipped with mechanical stirring. ) and 19 ml of water. Stirring until complete solubilization of the polymer.
Dans un malaxeur équipé d'arbres à came, on introduit 19,7 g d'une poudre de HKUST (Basolite C300) (représentant 90% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) ainsi que la polyvinylpyrrolidone solubilisée. On poursuit ensuite le malaxage jusqu'à l'obtention d'une pâte. In a kneader equipped with cam shafts, 19.7 g of a powder of HKUST (Basolite C300) (representing 90% by weight relative to the total quantity of powders introduced in said step a)) and the solubilized polyvinylpyrrolidone. The mixing is then continued until a paste is obtained.
Étape b) Step b)
On introduit la pâte dans une extrudeuse à piston de type rhéomètre capillaire (filière ø 3 mm) et on applique une pression suffisante afin d'obtenir un jonc. The paste is introduced into a capillary rheometer type piston extruder (die ø 3 mm) and a sufficient pressure is applied to obtain a rod.
Étape c) Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 16 heures à 80°C puis 120°C ou 200°C pendant 16 heures.  In order to remove the solvent, the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. or 200 ° C. for 16 hours.
Exemple 5 : Example 5
Étape a) Step a)
Dans un malaxeur équipé d'arbres à came, 1 ,2 g d'une poudre de méthocel K15M commercialisé par DOW (représentant 5% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)), 24 g d'une poudre de HKUST (Basolite C300) (représentant 95% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)) ainsi que 20 ml d'eau sont mélangés. On poursuit ensuite le malaxage jusqu'à l'obtention d'une pâte.  In a kneader equipped with cam shafts, 1.2 g of a methocel powder K15M marketed by Dow (representing 5% by weight relative to the total amount of powders introduced in said step a)), 24 g of a powder of HKUST (Basolite C300) (representing 95% by weight expressed relative to the total amount of powders introduced in said step a)) and 20 ml of water are mixed. The mixing is then continued until a paste is obtained.
Étape b) Step b)
On introduit la pâte dans une extrudeuse à piston de type rhéomètre capillaire (filière ø 3 mm) et on applique une pression suffisante afin d'obtenir un jonc. The paste is introduced into a capillary rheometer type piston extruder (die ø 3 mm) and a sufficient pressure is applied to obtain a rod.
Étape c) Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 16 heures à 80°C puis 120°C pendant 16 heures.  In order to remove the solvent, the extrudates are subjected to a heat treatment of 16 hours at 80 ° C. and then 120 ° C. for 16 hours.
Exemple 6 : Example 6
Étape a) Dans un malaxeur équipé d'arbres à came, 3, 1 g d'une poudre de méthocel K15M commercialisé par DOW Chemicals (représentant 5% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a)), 62,5 g (représentant 95% poids exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a) d'une poudre de SIM- I ainsi que 34,2 ml d'eau sont mélangées. On poursuit ensuite le malaxage jusqu'à l'obtention d'une pâte. Step a) In a kneader equipped with cam shafts, 3.1 g of a K15M methocel powder marketed by DOW Chemicals (representing 5% by weight relative to the total quantity of powders introduced in said stage a)), 62.5 g (95% by weight relative to the total amount of powders introduced in said step a) of a SIM-I powder and 34.2 ml of water are mixed. The mixing is then continued until a paste is obtained.
Étape b) Step b)
On introduit la pâte dans une extrudeuse à piston de type rhéomètre capillaire (filière ø 3 mm) et on applique une pression suffisante afin d'obtenir un jonc.  The paste is introduced into a capillary rheometer type piston extruder (die ø 3 mm) and a sufficient pressure is applied to obtain a rod.
Étape c) Step c)
Afin d'éliminer le solvant on applique aux extrudés un traitement thermique de 16 heures à 40°C puis 120°C pendant 16 heures.  In order to eliminate the solvent, the extrudates are subjected to a heat treatment of 16 hours at 40 ° C. and then 120 ° C. for 16 hours.
Les pourcentages poids de polymère et de matériau hybride organique-inorganique cristallisé utilisés dans les exemples ainsi que les caractéristiques des matériaux obtenus sont récapitulés dans le tableau 2 ci-dessous : The weight percentages of polymer and hybrid organic-inorganic crystallized material used in the examples as well as the characteristics of the materials obtained are summarized in Table 2 below:
La perte de microporosité est calculée en tenant compte de la dilution due à la présence de liant polymère dans le matériau final sous forme d'extrudé : le volume microporeux du matériau obtenu sous forme d'extrudé est comparé à celui de la poudre de MHOIC de départ, pondéré du facteur de dilution qui est égal au pourcentage massique de MHOIC présent dans la matériau obtenu sous forme d'extrudé.  The loss of microporosity is calculated taking into account the dilution due to the presence of polymeric binder in the final material in extruded form: the microporous volume of the material obtained in extruded form is compared with that of the MHOIC powder of starting, weighted dilution factor which is equal to the mass percentage of MHOIC present in the material obtained in the form of extruded.
Pour le matériau obtenu sous forme d'extrudé, la perte de microporosité = [(volume microporeux du MHOIC de départ x % massique de MHOIC présent dans le matériau final obtenu sous forme d'extrudé)/ 100 - volume microporeux du matériau final obtenu sous forme d'extrudé] x 100 / (volume microporeux du MHOIC de départ x % massique de MHOIC présent dans le matériau final obtenu sous forme d'extrudé)/100).
Figure imgf000019_0001
For the material obtained in extruded form, the loss of microporosity = [(microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100 - microporous volume of the final material obtained under extruded form] x 100 / (microporous volume of the starting MHOIC x mass% of MHOIC present in the final material obtained in extruded form) / 100).
Figure imgf000019_0001

Claims

REVENDICATIONS
1 . Matériau comprenant au moins un matériau hybride organique-inorganique cristallisé mis en forme sous forme d'extrudé avec une formulation liante comprenant au moins un liant polymère, ledit matériau étant constitué de 80 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 20% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau. 1. Material comprising at least one crystallized organic-inorganic hybrid material shaped in extruded form with a binder formulation comprising at least one polymeric binder, said material consisting of 80 to 99 wt.% Of at least one organic-inorganic hybrid material crystallized and from 1 to 20% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material.
2. Matériau selon la revendication 1 dans lequel ledit matériau hybride organique-inorganique cristallisé est de préférence choisi parmi les MOF, les ZIFs, les MILs et les IRMOFs, seuls ou en mélange. 2. The material of claim 1 wherein said hybrid organic-inorganic hybrid material is preferably selected from MOF, ZIFs, MILs and IRMOFs, alone or in admixture.
3. Matériau selon la revendication 2 dans lequel ledit matériau hybride organique-inorganique cristallisé est de préférence choisi parmi la liste suivante : SIM- 1 , HKUST, CAU- 1 , MOF-5, MOF-38, MOF-305, MOF-37, MOF- 12, IRMOF-2 à - 16, MIL-53, MIL-68, MIL- 101 , ZIF-8, ZIF- 1 1 , ZIF-67, ZIF-90. The material of claim 2 wherein said crystallized organic-inorganic hybrid material is preferably selected from the following list: SIM-1, HKUST, CAU-1, MOF-5, MOF-38, MOF-305, MOF-37 , MOF-12, IRMOF-2 to -16, MIL-53, MIL-68, MIL-101, ZIF-8, ZIF-11, ZIF-67, ZIF-90.
4. Matériau selon l'une des revendications 1 ou 2 dans lequel le(s)dit(s) liant(s) polymère(s) est (sont) choîsi(s) parmi les polyvinylpyrrolidones, les polymères cellulosiques et leurs dérivés choisis parmi les éthers de cellulose, les alcools polyvinyliques, les polyéthylènes glycols, les polyacrylamides, les polysaccharides, les polymères naturels et leurs dérivés, les polyesters, les polyamides et polyamides aromatiques, les polyéthers, les poly (aryéther), les polyuréthanes, les polysulfones, les polymères hétérocyliques choisis parmi les polyimides, les polyéthers imides, les polyesters imides, les polyamides imides, et les polybenzimidazoles. 4. Material according to one of claims 1 or 2 wherein said (s) binder (s) polymer (s) is (are) selected from polyvinylpyrrolidones, cellulosic polymers and their derivatives selected from cellulose ethers, polyvinyl alcohols, polyethylene glycols, polyacrylamides, polysaccharides, natural polymers and their derivatives, polyesters, aromatic polyamides and polyamides, polyethers, poly (aryether), polyurethanes, polysulfones, heterocylic polymers chosen from polyimides, polyether imides, polyester imides, polyamide imides, and polybenzimidazoles.
5. Matériau selon la revendication 4 dans lequel le(s)dit(s) iiant(s) polymère(s) est (sont) choisi(s) parmi les polyvinylpyrrolidones, les polyimides, les polymères cellulosiques. 5. Material according to claim 4 wherein the (s) said polymer (s) is (are) chosen (s) from polyvinylpyrrolidones, polyimides, cellulosic polymers.
6. Matériau selon l'une des revendications 1 à 5 constitué de 85 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 15% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau, 6. Material according to one of claims 1 to 5 consisting of 85 to 99% by weight of at least one crystallized organic-inorganic hybrid material and 1 to 15% by weight of at least one polymeric binder, the weight percentages being expressed relative to the total mass of said material,
7. Matériau selon la revendications 6 constitué de 90 à 99% poids d'au moins un matériau hybride organique-inorganique cristallisé et de 1 à 10% poids d'au moins un liant polymère, les pourcentages poids étant exprimés par rapport à la masse totale dudit matériau. 7. Material according to claim 6 consisting of 90 to 99% by weight of at least one crystallized organic-inorganic hybrid material and from 1 to 10% by weight of at least one polymeric binder, the weight percentages being expressed relative to the mass. total of said material.
8. Matériau selon l'une des revendications 1 à 7 se présentant sous forme d'extradés de diamètre compris entre 0,8 et 5 mm. 8. Material according to one of claims 1 to 7 in the form of extrudates with a diameter of between 0.8 and 5 mm.
9. Procédé de préparation du matériau selon l'une des revendications 1 à 8 comprenant au moins les étapes suivantes ; 9. Process for preparing the material according to one of claims 1 to 8 comprising at least the following steps;
a) une étape de mélange d'au moins 80 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC) avec au moins 1 à 20% poids d'une poudre d'au moins un polymère et un soivant pour obtenir un mélange, les pourcentages poids étant exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a), b) une étape de mise en forme par extrusion du mélange obtenu à l'issue de l'étape a), c) une étape de traitement thermique du matériau mis en forme obtenu à l'issue de l'étape b), ladite étape de traitement thermique étant réalisée à une température comprise entre 25 et 300°C, pendant une durée comprise entre 1 minute et 72 heures. a) a step of mixing at least 80 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) with at least 1 to 20% by weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total quantity of powders introduced in said step a), b) a step of shaping by extrusion of the mixture obtained at the end of the step a), c) a step of heat treatment of the shaped material obtained at the end of step b), said heat treatment step being carried out at a temperature of between 25 and 300 ° C., for a period of time between 1 minute and 72 hours.
10. Procédé de préparation selon la revendication 9 dans lequel on mélange dans l'étape a) au moins 85 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC) avec au moins 1 à 15% poids d'une poudre d'au moins un polymère et un solvant pour obtenir un mélange, les pourcentages poids étant exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a). 10. Preparation process according to claim 9 wherein in step a) at least 85 to 99 wt.% Of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) is mixed with at least 1 to 15 wt. % weight of a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a).
1 1 . Procédé de préparation selon la revendication 10 dans lequel on mélange dans l'étape a) au moins 90 à 99% poids d'une poudre d'au moins un matériau hybride organique-inorganique cristallisé (MHOIC) avec au moins 1 à 10% poids d'une poudre d'au moins un polymère et un solvant pour obtenir un mélange, les pourcentages poids étant exprimés par rapport à la quantité totale de poudres introduites dans ladite étape a). 1 1. Preparation process according to Claim 10, in which at least 90 to 99% by weight of a powder of at least one crystalline organic-inorganic hybrid material (MHOIC) is mixed in step a) with at least 1 to 10% by weight a powder of at least one polymer and a solvent to obtain a mixture, the weight percentages being expressed relative to the total amount of powders introduced in said step a).
12. Procédé de préparation selon l'une des revendications 9 à 1 1 dans lequel ladite étape de traitement thermique est effectuée sous gaz inerte ou sous vide. 12. Preparation process according to one of claims 9 to 11 wherein said heat treatment step is carried out under inert gas or under vacuum.
13. Procédé de préparation selon la revendication 12 dans lequel ladite étape de traitement thermique est effectuée sous air. 13. Preparation process according to claim 12 wherein said heat treatment step is carried out under air.
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US20130305920A1 (en) * 2011-02-14 2013-11-21 National University Of Singapore Preparation of Zeolitic Imidazolate Frameworks (ZIFs) - Polybenzimidazole Mixed-Matrix Composite and Application for Gas and Vapor Separation
CN107376880A (en) * 2017-07-27 2017-11-24 浙江理工大学 It is a kind of to be used to adsorb three-dimensional porous aeroges of ZIF 8/ of cellulose base of heavy metal ion and preparation method thereof
CN107376880B (en) * 2017-07-27 2019-11-15 浙江理工大学 Three-dimensional porous ZIF-8/ aeroge of a kind of cellulose base for adsorbing heavy metal ion and preparation method thereof
WO2021107992A1 (en) * 2019-11-26 2021-06-03 Exxonmobil Research And Engineering Company Metal-organic material extrudates, methods of making, and methods of use
CN115023283A (en) * 2019-11-26 2022-09-06 埃克森美孚技术与工程公司 Method for producing metal-organic framework extrudates
CN115023284A (en) * 2019-11-26 2022-09-06 埃克森美孚技术与工程公司 Metal-organic material extrudates, methods of making and methods of using
CN115023284B (en) * 2019-11-26 2024-02-02 埃克森美孚技术与工程公司 Metal-organic material extrudates, methods of manufacture and methods of use
CN115023283B (en) * 2019-11-26 2024-03-19 埃克森美孚技术与工程公司 Method for producing metal-organic framework extrudates
FR3124093A1 (en) * 2021-06-21 2022-12-23 Saint-Gobain Centre De Recherches Et D'etudes Europeen Process for making MOF product and grain powder into MOF product
WO2022269184A1 (en) * 2021-06-21 2022-12-29 Saint-Gobain Centre De Recherche Et D'etudes Europeen Process for producing a mof-based product and powder of grains composed of a mof-based product

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