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  • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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  • 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
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  • 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
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • 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
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  • 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.

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• 2010
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