EP2643085A1 - Novel im-21 organic-inorganic hybrid solid and process for preparing same - Google Patents

Novel im-21 organic-inorganic hybrid solid and process for preparing same

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Publication number
EP2643085A1
EP2643085A1 EP11801767.2A EP11801767A EP2643085A1 EP 2643085 A1 EP2643085 A1 EP 2643085A1 EP 11801767 A EP11801767 A EP 11801767A EP 2643085 A1 EP2643085 A1 EP 2643085A1
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EP
European Patent Office
Prior art keywords
solid
hybrid
process according
preparation process
organic
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EP11801767.2A
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German (de)
French (fr)
Inventor
David Peralta
Karin Barthelet
Gerthard PIRNGRUBER
Gérarld CHAPLAIS
Angélique SIMON-MASSERON
Joël Patarin
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IFP Energies Nouvelles IFPEN
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Centre National de la Recherche Scientifique CNRS
IFP Energies Nouvelles IFPEN
Universite de Haute Alsace
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Publication of EP2643085A1 publication Critical patent/EP2643085A1/en
Withdrawn legal-status Critical Current

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    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J20/28088—Pore-size distribution
    • B01J20/2809—Monomodal or narrow distribution, uniform pores
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B01J35/30—
    • B01J35/615—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc

Definitions

  • the present invention relates to a novel crystalline hybrid solid hybrid organic-inorganic mixed matrix, three-dimensional structure, and its preparation process.
  • Said new solid object of the present invention is called IM-21 in the following description.
  • the present invention also relates to the use of said IM-21 solid as catalyst or adsorbent.
  • MOFs Metal-Organic Frameworks
  • coordination polymers are porous crystalline solids in which the sub-networks of metal cations (dimers, trimers, tetramers, chain, plane) are connected to each other by organic molecules serving as multidentate ligands to form a two- or three-dimensional structure.
  • this class of materials makes it possible to create an immense number of new structures.
  • the known and particularly interesting hybrid materials are most often based on organic ligands consisting of di- or tricarboxylates or derivatives of pyridine.
  • the compound used as precursor of the ligand present in the solid according to the invention is 2,5-dihydroxyterephthalic acid (H 4 dhtp).
  • the inorganic entity acting as a connector is, for its part, zinc.
  • the present invention relates to a novel crystalline hybrid solid hybrid organic-inorganic matrix having a three-dimensional structure.
  • This new solid is called IM-21. It contains an inorganic network of zinc-based metal centers interconnected by deprotonated organic ligands consisting of the -0 2 C-C 6 H 2 - (O) 2 -C0 2 moiety.
  • deprotonated organic ligands consisting of the -0 2 C-C 6 H 2 - (O) 2 -C0 2 moiety.
  • the acid and hydroxide functions of 2,5-dihydroxyterephthalic acid of formula H0 2 CC 6 H 2 (OH) 2 -C O 2 H are deprotonated.
  • the IM-21 crystallized hybrid solid according to the present invention has an X-ray diffraction pattern including at least the lines listed in Table 1.
  • the relative intensity l / l 0 assigned to each d hW value is measured from the height of the corresponding diffraction peak.
  • the X-ray diffraction pattern of the crystallized hybrid solid IM-21 according to the invention comprises at least the lines with the values of d h ki given in Table 1. In the column of d h ki. the average values of inter-reticular distances in Angstroms (A) have been indicated. Each of these values shall be assigned the measurement error A (d h ki) of between ⁇ 0.3 A and ⁇ 0.01 A. Mean values of c, w, and relative intensities measured on an X-ray diffraction pattern of the IM-21 crystallized hybrid solid.
  • the relative intensity l / l 0 is given in relation to a relative intensity scale where a value of 100 is assigned to the most intense line of the X-ray diffraction pattern: f ⁇ 15; 15 ⁇ mf ⁇ 30; 30 ⁇ m ⁇ 85;F> 85.
  • the IM-21 crystallized hybrid solid according to the invention has a basic crystalline structure or topology which is characterized by its X-ray diffraction pattern given in FIG. 1.
  • Said solid has a chemical composition having the basic Zn 2 motif (-0 2 C- C 6 H 2 (O) 2 -C0 2 -). This pattern is repeated n times with generally greater than 100.
  • the IM-21 crystallized hybrid solid according to the invention has a three-dimensional structure in which the inorganic network of metal centers based on Zn 2+ cations acting as connectors are bonded to each other by deprotonated terephthalic ligands carrying two hydroxyl functions deprotonated on the aromatic ring in position 2 and 5 (-0 2 C- C 6 H 2 (O) 2 -C0 2 -).
  • the subject of the present invention is also a process for the preparation of said IM-21 hybrid crystalline hybrid with organic-inorganic mixed matrix.
  • This method comprises at least the following steps: i) the preparation, in an aqueous medium, of a reaction mixture containing at least one zinc precursor and 2,5-dihydroxyterephthalic acid (denoted H 4 dhtp) present in a solvent mixture comprising at least N, N dimethylformamide (DMF) and propanol (C 3 H 7 OH) in a proportion such that said reaction mixture has the following molar composition, based on a molar equivalent of the zinc element:
  • the zinc precursor is advantageously chosen from zinc (II) salts such as zinc chlorides, sulphates, acetates or nitrates.
  • said precursor used is a zinc nitrate.
  • 2,5-Dihydroxyterephthalic acid (H0 2 CC 6 H 2 - (OH) 2 -CO 2 H), dimethylformamide and propanol, preferentially propan-1-ol, are commercially available compounds.
  • the reaction mixture preferably has the following molar composition, based on a molar equivalent of the zinc element:
  • the solvothermal treatment according to said step ii) of the preparation process according to the invention is carried out under autogenous reaction pressure conditions. Said solvothermal treatment is preferably carried out at a temperature between 160 and 190 ° C. The duration of said treatment is between 8 and 72 hours, preferably between 10 and 30 hours.
  • the solid obtained at the end of said step ii) is an IM-21 crystallized hybrid solid having an X-ray diffraction pattern including at least the lines listed in Table 1.
  • the crystalline hybrid solid IM-21 obtained at the end of said step ii) is filtered and washed with one or more suitable solvents, in particular ⁇ , ⁇ -dimethylformamide (DMF) and ethanol. Then, according to said step iii), said solid is dried at a temperature between 20 ° C and 200 ° C, preferably between 20 and 100 ° C, more preferably between 20 and 80 ° C, for a period of between 1 and 24 hours, most often between 4 and 10 hours.
  • the crystalline hybrid solid IM-21 obtained at the end of said step iii) is in its crude synthesis form, that is to say in a form in which the porosity of said solid is not released from the presence of solvents. Said solid obtained in its raw synthesis form has an X-ray diffraction pattern including at least the lines listed in Table 1.
  • the solid obtained at the end of said step iv) of the preparation process according to the invention is a porous solid: it is devoid of any solvent and is dehydrated.
  • said step iv) is preceded by an exchange step of exchanging at least one solvent used for the implementation of said step i), preferentially DMF, present in the porosity of the IM-21 solid in its crude synthesis form, with a solvent preferably chosen from methanol, ethanol, isopropanol and acetonitrile.
  • a solvent preferably chosen from methanol, ethanol, isopropanol and acetonitrile.
  • said solvent is methanol.
  • Said exchange step generally consists in immersing said solid in its crude synthesis form, resulting from said step iii), in said solvent, preferably in methanol. The exchange is carried out at a temperature between room temperature and 10 ° C, preferably between 50 and 90 ° C for 1 to 15 days.
  • the solvent allowing the exchange is preferably renewed regularly.
  • the suspension containing the IM-21 solid exchanged in the solvent preferably in methanol, is filtered and then advantageously dried.
  • the drying is carried out at a temperature between room temperature and 100 ° C, preferably at room temperature, for a period of between 2 and 12 hours.
  • the present invention also relates to the use of said hybrid solid IM-21 as adsorbent or catalyst.
  • said IM-21 hybrid solid according to the invention is advantageously used in a process for separating carbon dioxide present in a gaseous mixture to be purified, such as synthesis gas, carbon dioxide, and the like. natural gas or combustion fumes.
  • Example 1 (Invention): Preparation of hybrid solid IM-21 hybrid with organic-inorganic mixed matrix
  • Examples 1.1 to 1.4 below illustrate different protocols for obtaining the porous IM-21 hybrid solid.
  • Example 1.1 The solid IM-21 in its as-synthesized form (crude IM-21) is heated for 12 hours at 300 ° C under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 326 m 2 / g.
  • Example 1.2 The solid IM-21 in its as-synthesized form (crude IM-21) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 180 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 354 m 2 / g.
  • Example 1.3 The solid IM-21 in its as-synthesized form (crude IM-21) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 350 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 489 m 2 / g.
  • Example 1.4 The solid IM-21 in its as-synthesized form (IM-21 m t) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 450 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 1030 m 2 / g.
  • the PTFE container containing the first batch is then transferred to an autoclave and then heated without stirring at 110 ° C for 24 hours.
  • the PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 120 ° C for 24 hours.
  • the PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 140 ° C for 24 hours.
  • the PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 160 ° C for 24 hours.

Abstract

A novel crystallized hybrid solid with an organic-inorganic mixed matrix is described that has a three-dimensional structure containing an inorganic lattice of zinc-based metal centres connected together by deprotonated organic ligands constituted by the species -O2C-C6H2-(O)2-CO2. This novel solid is called IM-21 and has an X-ray diffraction diagram as given below.

Description

NOUVEAU SOLIDE HYBRIDE ORGANIQUE-INORGANIQUE IM-21 ET SON PROCÉDÉ DE PRÉPARATION  NEW ORGANIC-INORGANIC HYBRID SOLID IM-21 AND PREPARATION METHOD THEREOF
Domaine technique de l'invention Technical field of the invention
La présente invention se rapporte à un nouveau solide hydride cristallisé à matrice mixte organique-inorganique, de structure tridimensionnelle, et à son procédé de préparation. Ledit nouveau solide, objet de la présente invention, est appelé IM-21 dans la suite de la description. La présente invention se rapporte également à l'utilisation dudit solide IM-21 comme catalyseur ou adsorbant. The present invention relates to a novel crystalline hybrid solid hybrid organic-inorganic mixed matrix, three-dimensional structure, and its preparation process. Said new solid object of the present invention is called IM-21 in the following description. The present invention also relates to the use of said IM-21 solid as catalyst or adsorbent.
Art antérieur Prior art
La famille des solides poreux, d'une importance incontestable autant dans des applications de la vie courante qu'industrielles, suscite encore et toujours un intérêt majeur dans les travaux de recherche réalisés dans le domaine des matériaux.  The family of porous solids, of unquestionable importance in both everyday and industrial applications, is still a major focus of research in the field of materials.
Depuis les années 1990, un intérêt particulier s'est manifesté pour des composés hybrides à matrice mixte organique-inorganique, aussi appelés MOFs (Metal-Organic Frameworks) ou polymères de coordination. Les MOFs sont des solides cristallisés poreux dans lesquels les sous-réseaux de cations métalliques (dimères, trimères, tétramères, chaîne, plan) sont connectés entre eux par des molécules organiques servant de ligands multidentates pour former une structure bi- ou tridimensionnelle.  Since the 1990s, there has been a particular interest in hybrids with mixed organic-inorganic matrix, also called MOFs (Metal-Organic Frameworks) or coordination polymers. MOFs are porous crystalline solids in which the sub-networks of metal cations (dimers, trimers, tetramers, chain, plane) are connected to each other by organic molecules serving as multidentate ligands to form a two- or three-dimensional structure.
Grâce à la diversité de combinaisons possibles entre le connecteur inorganique et le ligand organique, cette classe de matériaux permet de créer un nombre immense de nouvelles structures. Thanks to the diversity of possible combinations between the inorganic connector and the organic ligand, this class of materials makes it possible to create an immense number of new structures.
Néanmoins, parmi le grand nombre de structures qui ont déjà été synthétisées, seule une petite fraction possède une porosité accessible. Or, l'accessibilité des pores est une propriété essentielle pour l'utilisation de ces matériaux en tant que catalyseur ou adsorbant. Différentes raisons peuvent expliquer l'absence de porosité accessible dans les matériaux hybrides : soit la structure du matériau hybride est trop dense, soit l'ouverture des pores est trop petite. A ces deux explications, il peut arriver que dans certains cas, la structure cristalline du matériau hybride qui devrait théoriquement avoir des pores accessibles, possède des molécules de solvant et/ou des ligands organiques qui restent piégés dans la structure après la synthèse ce qui empêche la libération de la porosité.  Nevertheless, of the large number of structures that have already been synthesized, only a small fraction has an accessible porosity. However, the accessibility of the pores is an essential property for the use of these materials as a catalyst or adsorbent. Various reasons may explain the lack of accessible porosity in hybrid materials: either the structure of the hybrid material is too dense, or the opening of the pores is too small. To these two explanations, it may happen that in some cases, the crystalline structure of the hybrid material that theoretically should have accessible pores, has solvent molecules and / or organic ligands that remain trapped in the structure after synthesis which prevents the release of porosity.
Les matériaux hybrides connus et particulièrement intéressants sont le plus souvent à base de ligands organiques constitués de di- ou tricarboxylates ou des dérivés de la pyridine. Quelques ligands organiques fréquemment rencontrés sont notamment : bdc = benzène-1 ,4- dicarboxylate, btc = benzène-1 , 3, 5-tricarboxylate, ndc = naphtalène-2,6-dicarboxylate, H4dhtp = acide-2,5-dihydroxytéréphthalique bpy = 4,4'-bipyridine, hfipbb = 4,4'- (hexafluororisopropylidene)-bisbenzoate, cyclam = 1 ,4,8,11-tetraazacyclotetradecane. The known and particularly interesting hybrid materials are most often based on organic ligands consisting of di- or tricarboxylates or derivatives of pyridine. Some organic ligands frequently encountered are in particular: bdc = benzene-1,4-dicarboxylate, btc = benzene-1,3,5-tricarboxylate, ndc = naphthalene-2,6-dicarboxylate, H 4 dhtp = acid-2,5- bpy = 4,4'-bipyridine dihydroxyterephthalic, hfipbb = 4,4'- (hexafluororisopropylidene) -bisbenzoate, cyclam = 1, 4,8,11-tetraazacyclotetradecane.
Dans le cadre de la présente invention, le composé utilisé comme précurseur du ligand présent dans le solide selon l'invention est l'acide-2,5-dihydroxytéréphtalique (H4dhtp). L'entité inorganique jouant le rôle de connecteur est, quant à elle, le zinc. In the context of the present invention, the compound used as precursor of the ligand present in the solid according to the invention is 2,5-dihydroxyterephthalic acid (H 4 dhtp). The inorganic entity acting as a connector is, for its part, zinc.
Description de l'invention Description of the invention
La présente invention a pour objet un nouveau solide hybride cristallisé à matrice mixte organique-inorganique présentant une structure tridimensionnelle. Ce nouveau solide est appelé IM-21. Il contient un réseau inorganique de centres métalliques à base de zinc connectés entre eux par des ligands organiques déprotonés constitués par l'entité -02C- C6H2-(0)2-C02. Les fonctions acides et hydroxydes de l'acide-2,5-dihydroxytéréphtalique de formule H02C-C6H2-(OH)2-C02H sont déprotonées. The present invention relates to a novel crystalline hybrid solid hybrid organic-inorganic matrix having a three-dimensional structure. This new solid is called IM-21. It contains an inorganic network of zinc-based metal centers interconnected by deprotonated organic ligands consisting of the -0 2 C-C 6 H 2 - (O) 2 -C0 2 moiety. The acid and hydroxide functions of 2,5-dihydroxyterephthalic acid of formula H0 2 CC 6 H 2 (OH) 2 -C O 2 H are deprotonated.
Le solide hybride cristallisé IM-21 selon la présente invention présente un diagramme de diffraction des rayons X incluant au moins les raies inscrites dans le tableau 1. Ce diagramme de diffraction est obtenu par analyse radiocnstallographique au moyen d'un diffractomètre en utilisant la méthode classique des poudres avec le rayonnement Kcrt du cuivre (λ=1 ,5406Α). A partir de la position des pics de diffraction représentée par l'angle 2Θ, on calcule, en appliquant la relation de Bragg, les équidistances réticulaires dhki caractéristiques de l'échantillon. L'erreur de mesure A(dhki) sur dhk| est calculée grâce à la relation de Bragg en fonction de l'erreur absolue Δ(2Θ) affectée à la mesure de 2Θ. Une erreur absolue de Δ(2Θ) égale à ±0,2° est communément admise. L'intensité relative l/l0 affectée à chaque valeur de dhW est mesurée d'après la hauteur du pic de diffraction correspondant. Le diagramme de diffraction des rayons X du solide hybride cristallisé IM-21 selon l'invention comporte au moins les raies aux valeurs de dhki données dans le tableau 1. Dans la colonne des dhki. on a indiqué les valeurs moyennes des distances inter-réticulaires en Angstroms (A). Chacune de ces valeurs doit être affectée de l'erreur de mesure A(dhki) comprise entre ±0,3 A et ±0,01 A. Valeurs moyennes des c ,wet intensités relatives mesurées sur un diagramme de diffraction de rayons X du solide hybride cristallisé IM-21. The IM-21 crystallized hybrid solid according to the present invention has an X-ray diffraction pattern including at least the lines listed in Table 1. This diffraction pattern is obtained by radioctallographic analysis using a diffractometer using the conventional method. powders with copper Kcrt radiation (λ = 1, 5406Α). From the position of the diffraction peaks represented by the angle 2Θ, we calculate, by applying the Bragg relation, the reticular equidistances d h ki characteristics of the sample. Measurement error A (dhki) on d hk | is calculated by means of the Bragg relation as a function of the absolute error Δ (2Θ) assigned to the measurement of 2Θ. An absolute error of Δ (2Θ) equal to ± 0.2 ° is commonly accepted. The relative intensity l / l 0 assigned to each d hW value is measured from the height of the corresponding diffraction peak. The X-ray diffraction pattern of the crystallized hybrid solid IM-21 according to the invention comprises at least the lines with the values of d h ki given in Table 1. In the column of d h ki. the average values of inter-reticular distances in Angstroms (A) have been indicated. Each of these values shall be assigned the measurement error A (d h ki) of between ± 0.3 A and ± 0.01 A. Mean values of c, w, and relative intensities measured on an X-ray diffraction pattern of the IM-21 crystallized hybrid solid.
où F=fort ; m=moyen ; mf=moyen faible ; f=faible. L'intensité relative l/l0 est donnée en rapport à une échelle d'intensité relative où il est attribué une valeur de 100 à la raie la plus intense du diagramme de diffraction de rayons X : f<15 ; 15≤mf<30 ; 30≤m<85 ; F>85. where F = strong; m = average; mf = weak medium; w = weak. The relative intensity l / l 0 is given in relation to a relative intensity scale where a value of 100 is assigned to the most intense line of the X-ray diffraction pattern: f <15; 15≤mf <30; 30≤m <85;F> 85.
Le solide hybride cristallisé IM-21 s'indexe en système hexagonal P, avec comme paramètres de maille a = b = 23,0688 A, c = 15,9260 A, V = 7339,4 A3 et les angles q = β = 90°, γ = ηο°. The hybrid crystalline solid IM-21 indexes hexagonal system P, with the lattice parameters a = b = 23.0688 A, c = 15.9260 A, V = 7339.4 A 3 and the angles q = β = 90 °, γ = ηο °.
Le solide hybride cristallisé IM-21 selon l'invention présente une structure cristalline de base ou topologie qui est caractérisée par son diagramme de diffraction X donné par la figure 1. Ledit solide présente une composition chimique ayant pour motif de base Zn2(-02C- C6H2(0)2-C02-). Ce motif est répété n fois avec généralement supérieur à 100. The IM-21 crystallized hybrid solid according to the invention has a basic crystalline structure or topology which is characterized by its X-ray diffraction pattern given in FIG. 1. Said solid has a chemical composition having the basic Zn 2 motif (-0 2 C- C 6 H 2 (O) 2 -C0 2 -). This pattern is repeated n times with generally greater than 100.
Le solide hybride cristallisé IM-21 selon l'invention présente une structure tridimensionnelle dans laquelle le réseau inorganique de centres métalliques à base de cations Zn2+ jouant le rôle de connecteurs sont liés entre eux par des ligands téréphtaliques déprotonés portant deux fonctions hydroxydes déprotonées sur le cycle aromatique en position 2 et 5 (-02C- C6H2(0)2-C02-). The IM-21 crystallized hybrid solid according to the invention has a three-dimensional structure in which the inorganic network of metal centers based on Zn 2+ cations acting as connectors are bonded to each other by deprotonated terephthalic ligands carrying two hydroxyl functions deprotonated on the aromatic ring in position 2 and 5 (-0 2 C- C 6 H 2 (O) 2 -C0 2 -).
La présente invention a également pour objet un procédé de préparation dudit solide hybride cristallisé IM-21 à matrice mixte organique-inorganique. Ce procédé comprend au moins les étapes suivantes : i) la préparation, en milieu aqueux, d'un mélange réactionnel contenant au moins un précurseur de zinc et de l'acide 2,5-dihydroxytéréphthalique (noté H4dhtp) présents dans un mélange de solvants comprenant au moins du N,N- diméthylformamide (DMF) et du propanol (C3H7OH) dans une proportion telle que ledit mélange réactionnel présente la composition molaire suivante, basée sur un équivalent molaire de l'élément zinc : The subject of the present invention is also a process for the preparation of said IM-21 hybrid crystalline hybrid with organic-inorganic mixed matrix. This method comprises at least the following steps: i) the preparation, in an aqueous medium, of a reaction mixture containing at least one zinc precursor and 2,5-dihydroxyterephthalic acid (denoted H 4 dhtp) present in a solvent mixture comprising at least N, N dimethylformamide (DMF) and propanol (C 3 H 7 OH) in a proportion such that said reaction mixture has the following molar composition, based on a molar equivalent of the zinc element:
1 Zn : 0,1 - 2 H4dhtp : 1 - 50 H20 : 3 -10 C3H7OH : 50 - 300 DMF le traitement solvothermal dudit mélange réactionnel à une température comprise entre 150°C et 290°C pour obtenir ledit solide hybride cristallisé IM- 21 sous sa forme brute de synthèse, 1 Zn: 0.1 - 2 H 4 dhtp: 1 - 50 H 2 O: 3 -10 C 3 H 7 OH: 50 - 300 DMF the solvothermal treatment of said reaction mixture at a temperature between 150 ° C and 290 ° C to obtain said IM-21 crystallized hybrid solid in its crude synthesis form,
iii) la filtration, le lavage et le séchage dudit solide hybride cristallisé IM-21 , iv) le traitement thermique dudit solide hybride cristallisé IM-21 issu de ladite étape iii).  iii) filtration, washing and drying of said IM-21 crystallized hybrid solid, iv) heat treatment of said IM-21 crystallized hybrid solid resulting from said step iii).
Conformément à ladite étape i) du procédé de préparation du solide hybride cristallisé IM-21 selon l'invention, le précurseur de zinc est avantageusement choisi parmi les sels de zinc (II) tels que les chlorures, sulfates, acétates ou nitrates de zinc. Très préférentiellement, ledit précurseur utilisé est un nitrate de zinc. L'acide 2,5-dihydroxytéréphthalique (H02C-C6H2- (OH)2-C02H), le diméthylformamide et le propanol, préférentiellement le propan-1-ol, sont des composés disponibles commercialement. According to said step i) of the process for preparing the crystallized hybrid solid IM-21 according to the invention, the zinc precursor is advantageously chosen from zinc (II) salts such as zinc chlorides, sulphates, acetates or nitrates. Very preferably, said precursor used is a zinc nitrate. 2,5-Dihydroxyterephthalic acid (H0 2 CC 6 H 2 - (OH) 2 -CO 2 H), dimethylformamide and propanol, preferentially propan-1-ol, are commercially available compounds.
Conformément à ladite étape i) du procédé de préparation selon l'invention, le mélange réactionnel présente préférentiellement la composition molaire suivante, basée sur un équivalent molaire de l'élément zinc : According to said step i) of the preparation process according to the invention, the reaction mixture preferably has the following molar composition, based on a molar equivalent of the zinc element:
1 Zn : 0,2 - 0,7 H4dhtp : 10 - 40 H20 : 5 -9 C3H7OH : 100 - 150 DMF1 Zn: 0.2 - 0.7 H 4 dhtp: 10 - 40 H 2 O: 5 -9 C 3 H 7 OH: 100 - 150 DMF
Le traitement solvothermal conformément à ladite étape ii) du procédé de préparation selon l'invention est mis en œuvre dans des conditions de pression de réaction autogène. Ledit traitement solvothermal est préférentiellement réalisé à une température comprise entre 160 et 190°C. La durée dudit traitement est comprise entre 8 et 72 heures, de préférence entre 10 et 30 heures. Le solide obtenu à l'issue de ladite étape ii) est un solide hybride cristallisé IM-21 présentant un diagramme de diffraction des rayons X incluant au moins les raies inscrites dans le tableau 1. The solvothermal treatment according to said step ii) of the preparation process according to the invention is carried out under autogenous reaction pressure conditions. Said solvothermal treatment is preferably carried out at a temperature between 160 and 190 ° C. The duration of said treatment is between 8 and 72 hours, preferably between 10 and 30 hours. The solid obtained at the end of said step ii) is an IM-21 crystallized hybrid solid having an X-ray diffraction pattern including at least the lines listed in Table 1.
Le solide hybride cristallisé IM-21 obtenu à l'issue de ladite étape ii) est filtré, lavé avec un ou des solvants appropriés, notamment le Ν,Ν-diméthylformamide (DMF) et l'éthanol. Puis, conformément à ladite étape iii), ledit solide est séché à une température comprise entre 20°C et 200°C, de préférence entre 20 et 100°C, de manière encore plus préférée entre 20 et 80°C, pendant une durée variant entre 1 et 24 heures, le plus souvent entre 4 et 10 heures. Le solide hybride cristallisé IM-21 obtenu à l'issue de ladite étape iii) se présente sous sa forme brute de synthèse, c'est-à-dire sous une forme dans laquelle la porosité dudit solide n'est pas libérée de la présence de solvants. Ledit solide obtenu sous sa forme brute de synthèse présente un diagramme de diffraction des rayons X incluant au moins les raies inscrites dans le tableau 1. The crystalline hybrid solid IM-21 obtained at the end of said step ii) is filtered and washed with one or more suitable solvents, in particular Ν, Ν-dimethylformamide (DMF) and ethanol. Then, according to said step iii), said solid is dried at a temperature between 20 ° C and 200 ° C, preferably between 20 and 100 ° C, more preferably between 20 and 80 ° C, for a period of between 1 and 24 hours, most often between 4 and 10 hours. The crystalline hybrid solid IM-21 obtained at the end of said step iii) is in its crude synthesis form, that is to say in a form in which the porosity of said solid is not released from the presence of solvents. Said solid obtained in its raw synthesis form has an X-ray diffraction pattern including at least the lines listed in Table 1.
De manière à libérer la porosité dudit solide IM-21 issu de ladite étape iii), celui-ci est soumis à un traitement thermique réalisé à une température comprise entre 150 et 500°C. La durée dudit traitement thermique est préférentiellement comprise entre 1 heure et 3 jours, de préférence entre 5 et 24 heures. Le solide obtenu à l'issue de ladite étape iv) du procédé de préparation selon l'invention est un solide poreux : il est dépourvu de tout solvant et est déshydraté.  In order to release the porosity of said IM-21 solid resulting from said step iii), it is subjected to a heat treatment carried out at a temperature between 150 and 500 ° C. The duration of said heat treatment is preferably between 1 hour and 3 days, preferably between 5 and 24 hours. The solid obtained at the end of said step iv) of the preparation process according to the invention is a porous solid: it is devoid of any solvent and is dehydrated.
Selon un mode de réalisation préférée du procédé selon l'invention, ladite étape iv) est précédée d'une étape d'échange consistant à échanger au moins un solvant utilisé pour la mise en œuvre de ladite étape i), préférentiellement le DMF, présent dans la porosité du solide IM-21 sous sa forme brute de synthèse, par un solvant préférentiellement choisi parmi le méthanol, l'éthanol, l'isopropanol et l'acétonitrile. De manière très préférée, ledit solvant est le méthanol. Ladite étape d'échange consiste généralement à plonger ledit solide sous sa forme brute de synthèse, issu de ladite étape iii), dans ledit solvant, préférentiellement dans le méthanol. L'échange est effectué à une température comprise entre la température ambiante et 10°C, de préférence entre 50 et 90°C pendant 1 à 15 jours. Le solvant permettant l'échange est préférentiellement régulièrement renouvelé. A l'issue de ladite étape d'échange, la suspension contenant le solide IM-21 échangé dans le solvant, préférentiellement dans le méthanol, est filtrée puis avantageusement séchée. Le séchage est opéré à une température comprise entre la température ambiante et 100°C, de préférence à température ambiante, pendant une durée comprise entre 2 et 12 heures.  According to a preferred embodiment of the process according to the invention, said step iv) is preceded by an exchange step of exchanging at least one solvent used for the implementation of said step i), preferentially DMF, present in the porosity of the IM-21 solid in its crude synthesis form, with a solvent preferably chosen from methanol, ethanol, isopropanol and acetonitrile. Very preferably, said solvent is methanol. Said exchange step generally consists in immersing said solid in its crude synthesis form, resulting from said step iii), in said solvent, preferably in methanol. The exchange is carried out at a temperature between room temperature and 10 ° C, preferably between 50 and 90 ° C for 1 to 15 days. The solvent allowing the exchange is preferably renewed regularly. At the end of said exchange step, the suspension containing the IM-21 solid exchanged in the solvent, preferably in methanol, is filtered and then advantageously dried. The drying is carried out at a temperature between room temperature and 100 ° C, preferably at room temperature, for a period of between 2 and 12 hours.
La présente invention a également pour objet l'utilisation dudit solide hybride IM-21 comme adsorbant ou catalyseur. En particulier, utilisé en tant qu'adsorbant, ledit solide hybride IM- 21 selon l'invention est avantageusement mis en œuvre dans un procédé de séparation de dioxyde de carbone présent dans un mélange gazeux à purifier, tel que le gaz de synthèse, le gaz naturel ou les fumées de combustion.  The present invention also relates to the use of said hybrid solid IM-21 as adsorbent or catalyst. In particular, used as an adsorbent, said IM-21 hybrid solid according to the invention is advantageously used in a process for separating carbon dioxide present in a gaseous mixture to be purified, such as synthesis gas, carbon dioxide, and the like. natural gas or combustion fumes.
L'invention est illustrée par les exemples suivants qui ne présentent, en aucun cas, un caractère limitatif. Exemple 1 (invention) : Préparation du solide hybride IM-21 à matrice mixte organique- inorganique The invention is illustrated by the following examples, which in no way present a limiting character. Example 1 (Invention): Preparation of hybrid solid IM-21 hybrid with organic-inorganic mixed matrix
9,73 g (133,1 mmol) de Ν,Ν-diméthylformamide (DMF) et 0,51 g (28,5 mmol) d'eau distillée sont placés dans un récipient en PTFE de 22,58 ml_ de volume intérieur. 0,29 g (1 mmol) de nitrate de zinc hexahydraté (Sigma Aldrich) est ajouté. Le mélange est agité pendant 5 minutes à l'aide d'un agitateur magnétique. 0,10 g (0,5 mmol) d'acide 2,5- dihydroxytérephthalique (H4dhtp) (Sigma Aldrich) est alors ajouté. Le mélange est agité pendant 5 minutes. Après homogénéisation, 0,41 g (6,9 mmol) de propan-1-ol (Alfa Aesar) est ajouté. La composition molaire du mélange obtenu est : 1 ,00 nitrate de zinc : 0,5 H4dhtp : 133,1 DMF : 34,5 H20 : 6,9 propan-1-ol. Le récipient en PTFE est alors transvasé dans un autoclave puis est chauffé sans agitation à 160°C pendant 24 heures. Après refroidissement, le solide cristallisé obtenu est filtré, lavé au DMF puis à l'éthanol. Après séchage sous air à 50°C pendant environ 6 heures, un solide cristallisé sous forme de poudre cristalline, correspondant au solide sous sa forme brute de synthèse, est obtenu et présente un diagramme de diffraction de rayons X incluant les raies inscrites dans le tableau 1. Ce solide est noté IM-21brut. 9.73 g (133.1 mmol) of Ν, Ν-dimethylformamide (DMF) and 0.51 g (28.5 mmol) of distilled water are placed in a PTFE container of 22.58 ml of internal volume. 0.29 g (1 mmol) of zinc nitrate hexahydrate (Sigma Aldrich) is added. The mixture is stirred for 5 minutes with a magnetic stirrer. 0.10 g (0.5 mmol) of 2,5-dihydroxytephthalic acid (H 4 dhtp) (Sigma Aldrich) is then added. The mixture is stirred for 5 minutes. After homogenization, 0.41 g (6.9 mmol) of propan-1-ol (Alfa Aesar) is added. The molar composition of the resulting mixture is: 1.00 zinc nitrate: 0.5 H 4 dhtp: 133.1 DMF: 34.5 H 2 0: 6.9 propan-1-ol. The PTFE container is then transferred to an autoclave and then heated without stirring at 160 ° C for 24 hours. After cooling, the crystallized solid obtained is filtered, washed with DMF and then with ethanol. After drying in air at 50 ° C. for approximately 6 hours, a crystalline solid in the form of crystalline powder, corresponding to the solid in its crude synthesis form, is obtained and has an X-ray diffraction pattern including the lines shown in the table. 1. This solid is noted IM-21 crude .
Les exemples 1.1 à 1.4 suivants illustrent différents protocoles d'obtention du solide hybride IM-21 poreux.  Examples 1.1 to 1.4 below illustrate different protocols for obtaining the porous IM-21 hybrid solid.
Exemple 1.1 : Le solide IM-21 sous sa forme brute de synthèse (IM-21brut) est chauffé 12 heures à 300 °C sous vide. On obtient le solide IM-21 poreux. Il présente une surface spécifique évaluée par adsorption d'azote à 77 K et calculée par la méthode BET égale à 326 m2/g. Example 1.1: The solid IM-21 in its as-synthesized form (crude IM-21) is heated for 12 hours at 300 ° C under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 326 m 2 / g.
Exemple 1.2 : Le solide IM-21 sous sa forme brute de synthèse (IM-21 brut) est immergé dans du méthanol à 70°C pour une durée de dix jours. Le solide est filtré puis chauffé 12 heures à 180°C sous vide. On obtient le solide IM-21 poreux. Il présente une surface spécifique évaluée par adsorption d'azote à 77 K et calculée par la méthode BET égale à 354 m2/g.Example 1.2: The solid IM-21 in its as-synthesized form (crude IM-21) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 180 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 354 m 2 / g.
Exemple 1.3 : Le solide IM-21 sous sa forme brute de synthèse (IM-21 brut) est immergé dans du méthanol à 70°C pour une durée de dix jours. Le solide est filtré puis chauffé 12 heures à 350°C sous vide. On obtient le solide IM-21 poreux. Il présente une surface spécifique évaluée par adsorption d'azote à 77 K et calculée par la méthode BET égale à 489 m2/g.Example 1.3: The solid IM-21 in its as-synthesized form (crude IM-21) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 350 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 489 m 2 / g.
Exemple 1.4 : Le solide IM-21 sous sa forme brute de synthèse (IM-21 mt) est immergé dans du méthanol à 70°C pour une durée de dix jours. Le solide est filtré puis chauffé 12 heures à 450°C sous vide. On obtient le solide IM-21 poreux. Il présente une surface spécifique évaluée par adsorption d'azote à 77 K et calculée par la méthode BET égale à 1030 m2/g. Exemple 2 Example 1.4: The solid IM-21 in its as-synthesized form (IM-21 m t) is immersed in methanol at 70 ° C for a period of ten days. The solid is filtered and then heated for 12 hours at 450 ° C. under vacuum. The porous IM-21 solid is obtained. It has a specific surface area evaluated by nitrogen adsorption at 77 K and calculated by the BET method equal to 1030 m 2 / g. Example 2
Trois lots de solides sont préparés selon le protocole suivant :  Three batches of solids are prepared according to the following protocol:
9,73 g (133,1 mmol) de Ν,Ν-diméthylformamide (DMF) et 0,51 g (28,5 mmol) d'eau distillée sont placés dans un récipient en PTFE de 22,58 mL de volume intérieur. 0,29 g (1 mmol) de nitrate de zinc hexahydraté (Sigma Aldrich) est ajouté. Le mélange est agité pendant 5 minutes à l'aide d'un agitateur magnétique. 0,10 g (0,5 mmol) d'acide 2,5- dihydroxytérephthalique (H4dhtp) (Sigma Aldrich) est alors ajouté. Le mélange est agité pendant 5 minutes. Après homogénéisation, 0,41 g (6,9 mmol) de propan-1-ol (Alfa Aesar) est ajouté. La composition molaire du mélange obtenu est : 1 ,00 nitrate de zinc : 0,5 H4dhtp : 133, 1 DMF : 34,5 H20 : 6,9 propan-1 -ol.  9.73 g (133.1 mmol) of Ν, Ν-dimethylformamide (DMF) and 0.51 g (28.5 mmol) of distilled water are placed in a PTFE container of 22.58 mL of interior volume. 0.29 g (1 mmol) of zinc nitrate hexahydrate (Sigma Aldrich) is added. The mixture is stirred for 5 minutes with a magnetic stirrer. 0.10 g (0.5 mmol) of 2,5-dihydroxytephthalic acid (H4dhtp) (Sigma Aldrich) is then added. The mixture is stirred for 5 minutes. After homogenization, 0.41 g (6.9 mmol) of propan-1-ol (Alfa Aesar) is added. The molar composition of the mixture obtained is: 1.00 zinc nitrate: 0.5 H4dhtp: 133, 1 DMF: 34.5 H20: 6.9 propan-1 -ol.
Le récipient en PTFE contenant le premier lot est alors transvasé dans un autoclave puis est chauffé sans agitation à 110°C pendant 24 heures.  The PTFE container containing the first batch is then transferred to an autoclave and then heated without stirring at 110 ° C for 24 hours.
Le récipient en PTFE contenant le deuxième lot est alors transvasé dans un autoclave puis est chauffé sans agitation à 120°C pendant 24 heures.  The PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 120 ° C for 24 hours.
Le récipient en PTFE contenant le deuxième lot est alors transvasé dans un autoclave puis est chauffé sans agitation à 140°C pendant 24 heures. The PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 140 ° C for 24 hours.
Le récipient en PTFE contenant le deuxième lot est alors transvasé dans un autoclave puis est chauffé sans agitation à 160°C pendant 24 heures.  The PTFE container containing the second batch is then transferred to an autoclave and then heated without stirring at 160 ° C for 24 hours.
Après refroidissement de chaque lot, le solide cristallisé obtenu est filtré, lavé au DMF puis à l'éthanol. Après séchage sous air à 50°C pendant environ 6 heures, un solide cristallisé sous forme de poudre cristalline, correspondant au solide sous sa forme brute de synthèse, est obtenu. Les diagrammes de diffraction de rayons X sont présentés Fig.2. Le diagramme de diffraction X simulé de la CPO-27 est également représenté pour référence.  After cooling each batch, the crystallized solid obtained is filtered, washed with DMF and then with ethanol. After drying in air at 50 ° C. for approximately 6 hours, a crystalline solid in the form of crystalline powder, corresponding to the solid in its crude synthetic form, is obtained. The X-ray diffraction diagrams are shown in Fig.2. The simulated X-ray diffraction pattern of CPO-27 is also shown for reference.
On voit clairement sur la Fig.2 que pour une température de traitement solvothermale comprise entre 110°C et 140°C, les solides obtenus sont un mélange de CPO-27 et de IM- It is clearly seen in FIG. 2 that for a solvothermal treatment temperature of between 110 ° C. and 140 ° C., the solids obtained are a mixture of CPO-27 and IM-
21. A 160°C, le solide IM-21 est obtenu pur. 21. At 160 ° C., the IM-21 solid is obtained pure.

Claims

REVENDICATIONS
1. Solide hybride cristallisé à matrice mixte organique-inorganique IM-21 , de structure tridimensionnelle, contenant un réseau inorganique de centres métalliques à base de zinc connectés entre eux par des ligands organiques déprotonés constitués par l'entité -02C- C6H2-(0)2-C02, ledit solide présentant un diagramme de diffraction des rayons X incluant au moins les raies inscrites dans le tableau ci-dessous : 1. Crystalline hybrid solid hybrid with an IM-21 organic-inorganic mixed matrix, of three-dimensional structure, containing an inorganic network of zinc-based metal centers interconnected by deprotonated organic ligands consisting of the -O 2 C-C 6 entity. H 2 - (0) 2 -C0 2 , said solid having an X-ray diffraction pattern including at least the lines listed in the table below:
où F=fort ; m=moyen ; mf=moyen faible ; f=faible, l'intensité relative l/l0 étant donnée en rapport à une échelle d'intensité relative où il est attribué une valeur de 100 à la raie la plus intense du diagramme de diffraction de rayons X : f<15 ; 15≤mf<30 ; 30≤m<85 ; F≥85. where F = strong; m = average; mf = weak medium; f = low, the relative intensity l / l 0 being given in relation to a relative intensity scale where a value of 100 is assigned to the most intense line of the X-ray diffraction pattern: f <15; 15≤mf <30; 30≤m <85; F≥85.
2. Solide hybride cristallisé IM-21 selon la revendication 1 tel qu'il s'indexe en système hexagonal P, avec comme paramètres de maille a = b = 23,0688 A, c = 15,9260 A, V = 7339,4 A3 et les angles q = β = 90°, y = 120°. 2. Crystallized hybrid hybrid IM-21 according to claim 1 as it is indexed in hexagonal system P, with as parameters of mesh a = b = 23.0688 A, c = 15.9260 A, V = 7339.4 At 3 and angles q = β = 90 °, y = 120 °.
3. Solide hybride cristallisé IM-21 selon la revendication 1 ou la revendication 2 tel qu'il présente une composition chimique ayant pour motif de base Zn2(-02C-C6H2(0)2-C02-).3. crystalline hybrid hybrid IM-21 according to claim 1 or claim 2 as it has a chemical composition having the basic pattern Zn 2 (-0 2 CC 6 H 2 (0) 2 -C0 2 -).
4. Procédé de préparation d'un solide hybride cristallisé IM-21 à matrice mixte organique- inorganique comprenant au moins les étapes suivantes : 4. Process for the preparation of an IM-21 crystallized hybrid solid hybrid organic-inorganic comprising at least the following steps:
i) la préparation, en milieu aqueux, d'un mélange réactionnel contenant au moins un précurseur de zinc et de l'acide 2,5-dihydroxytéréphthalique (H dhtp) présents dans un mélange de solvants comprenant au moins du Ν,Ν-diméthylformamide (DMF) et du propanol (C3H7OH) dans une proportion telle que ledit mélange réactionnel présente la composition molaire suivante, basée sur un équivalent molaire de l'élément zinc : i) the preparation, in an aqueous medium, of a reaction mixture containing at least one zinc precursor and 2,5-dihydroxyterephthalic acid (H dhtp) present in a solvent mixture comprising at least Ν, Ν-dimethylformamide; (DMF) and propanol (C 3 H 7 OH) in a proportion such that said reaction mixture has the following molar composition, based on a molar equivalent of the zinc element:
1 Zn : 0,1 - 2 H4dhtp : 1 - 50 H20 : 3 -10 C3H7OH : 50 - 300 DMF ii) le traitement solvothermal dudit mélange réactionnel à une température comprise entre 150°C et 290°C pour obtenir ledit solide hybride cristallisé IM-21 sous sa forme brute de synthèse, 1 Zn: 0.1 - 2 H 4 dhtp: 1 - 50 H 2 0: 3 -10 C 3 H 7 OH: 50 - 300 DMF ii) the solvothermal treatment of said reaction mixture at a temperature between 150 ° C and 290 ° C ° C to obtain said IM-21 crystallized hybrid solid in its crude synthesis form,
iii) la filtration, le lavage et le séchage dudit solide hybride cristallisé IM-21 ,  iii) filtering, washing and drying said IM-21 crystallized hybrid solid,
iv) le traitement thermique dudit solide hybride cristallisé IM-21 issu de ladite étape iii). iv) heat treating said IM-21 crystallized hybrid solid resulting from said step iii).
5. Procédé de préparation selon la revendication 4 tel que ledit mélange réactionnel présente la composition molaire suivante, basée sur un équivalent molaire de l'élément zinc : The preparation process according to claim 4, wherein said reaction mixture has the following molar composition, based on a molar equivalent of the zinc element:
1 Zn : 0,2 - 0,7 H4dhtp : 10 - 40 H20 : 5 -9 C3H7OH : 100 - 150 DMF1 Zn: 0.2 - 0.7 H 4 dhtp: 10 - 40 H 2 O: 5 -9 C 3 H 7 OH: 100 - 150 DMF
6. Procédé de préparation selon la revendication 4 ou la revendication 5 tel que ledit traitement solvothermal est réalisé à une température comprise entre 160 et 190°C. 6. Preparation process according to claim 4 or claim 5 such that said solvothermal treatment is carried out at a temperature between 160 and 190 ° C.
7. Procédé de préparation selon l'une des revendications 4 à 6 tel que la durée dudit traitement solvothermal est comprise entre 8 et 72 heures.  7. Preparation process according to one of claims 4 to 6 such that the duration of said solvothermal treatment is between 8 and 72 hours.
8. Procédé de préparation selon l'une des revendications 4 à 7 tel que ledit traitement thermique est réalisé à une température comprise entre 150 et 500°C.  8. Preparation process according to one of claims 4 to 7 such that said heat treatment is carried out at a temperature between 150 and 500 ° C.
9. Procédé de préparation selon l'une des revendications 4 à 8 tel que la durée dudit traitement thermique est comprise entre 1 heure et 3 jours.  9. Preparation process according to one of claims 4 to 8 such that the duration of said heat treatment is between 1 hour and 3 days.
10. Procédé de préparation selon l'une des revendications 4 à 9 tel que le solide obtenu à l'issue de ladite étape iv) est un solide poreux. 10. Preparation process according to one of claims 4 to 9 such that the solid obtained at the end of said step iv) is a porous solid.
11. Procédé de préparation selon l'une des revendications 4 à 10 tel que ladite étape iv) est précédée d'une étape d'échange consistant à échanger au moins un solvant utilisé pour la mise en oeuvre de ladite étape i), présent dans la porosité du solide IM-21 sous sa forme brute de synthèse, par un solvant choisi parmi le méthanol, Péthanol, l'isopropanol et Pacétonitrile.  11. A method of preparation according to one of claims 4 to 10 such that said step iv) is preceded by an exchange step of exchanging at least one solvent used for the implementation of said step i), present in the porosity of the solid IM-21 in its crude synthesis form, with a solvent chosen from methanol, ethanol, isopropanol and acetonitrile.
12. Procédé de préparation selon la revendication 11 tel que ladite étape d'échange est effectuée à une température comprise entre la température ambiante et 110°C pendant 1 à 15 jours. 12. Preparation process according to claim 11 wherein said exchange step is carried out at a temperature between room temperature and 110 ° C for 1 to 15 days.
13. Utilisation du solide hybride cristallisé IM-21 selon l'une des revendications 1 à 3 ou préparé selon le procédé selon l'une des revendications 4 à 12 comme adsorbant ou catalyseur. 13. Use of crystalline hybrid solid IM-21 according to one of claims 1 to 3 or prepared according to the process according to one of claims 4 to 12 as adsorbent or catalyst.
EP11801767.2A 2010-11-26 2011-11-23 Novel im-21 organic-inorganic hybrid solid and process for preparing same Withdrawn EP2643085A1 (en)

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