EP1954395A1 - Materiaux structurels metallo-organiques du sous-groupe iii - Google Patents

Materiaux structurels metallo-organiques du sous-groupe iii

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Publication number
EP1954395A1
EP1954395A1 EP06819465A EP06819465A EP1954395A1 EP 1954395 A1 EP1954395 A1 EP 1954395A1 EP 06819465 A EP06819465 A EP 06819465A EP 06819465 A EP06819465 A EP 06819465A EP 1954395 A1 EP1954395 A1 EP 1954395A1
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EP
European Patent Office
Prior art keywords
acid
metal
dicarboxylic acid
organic compound
compound
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EP06819465A
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German (de)
English (en)
Inventor
Markus Schubert
Ulrich Müller
Stefan Marx
Rainer Senk
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BASF SE
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BASF SE
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Publication of EP1954395A1 publication Critical patent/EP1954395A1/fr
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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
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • 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
    • 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
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • 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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/35—Scandium
    • 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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/36—Yttrium
    • 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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a process for the preparation of a porous organometallic framework material and to the use of the prepared framework materials.
  • Organometallic frameworks are known in the art. These typically contain at least one at least one metal ion coordinated at least bidentate organic compound.
  • organometallic frameworks are described, for example, in US Pat. No. 5,648,508, EP-A 0 790 253, M.O. Keeffe, J. SoI. State Chem., 152 (2000), 3-20; Li, H., et al., Nature 402 (1999), 276; M. Eddaoudi, Topics in Catalysis 9 (1999), 105-11 1; Chen et al., Science 291 (2001), 1021-1023 and DE-A 101 1 1 230.
  • MOF organometallic frameworks
  • a metal salt is reacted with the at least bidentate organic compound, such as, for example, a dicarboxylic acid, and elevated pressure and elevated temperature.
  • a metal salt is reacted with the at least bidentate organic compound, such as, for example, a dicarboxylic acid, and elevated pressure and elevated temperature.
  • a pressure vessel such as an autoclave
  • elevated pressure and elevated temperature is often achieved by transferring the reaction mixture into a pressure vessel, such as an autoclave, and then closing it, so that a corresponding pressure is generated in the reaction space of the pressure vessel when the temperature increases. Often these temperatures are above 200 ° C.
  • Such reaction conditions are often referred to in the literature as hydrothermal conditions.
  • One problem may be that because of the use of a metal salt, the counterion to the metal cation (for example, nitrate) remaining after forming the organometallic framework material in the reaction medium must be separated from the framework material.
  • the metal cation for example, nitrate
  • the formed porous organometallic framework material may differ significantly from framework materials which are composed of the same metal ion and the same at least bidentate organic compound, but have been produced in a different way.
  • this observation also makes it possible to prepare framework materials based on a suitable variation of the preparation conditions which contain known metals or organic compounds unknown to frameworks and which may have properties which are particularly suitable for certain fields of use.
  • organometallic frameworks are those in which the metal ion originates from the third subgroup of the periodic table.
  • ES-A 2200681 produces organometallic rare earth disulfonates under hydrothermal conditions.
  • T.M. Reineke et al. deal with organometallic frameworks based on terbium (see, for example, J. Am. Chem. Soc., 121 (1999), 1651-1657; Angew. Chem. 11: 1 (1999), 2712-2716).
  • Porous metal organic frameworks based on praseodymium, europium and terbium are described by X. Zheng et al., Eur. J. Inorg. Chem. 2004, 3262-3268.
  • organometallic frameworks based on the above metal ions but having properties that may be particularly advantageous for certain applications.
  • Such fields of application may be the storage, separation or controlled release of substances, in particular of gases, or in connection with chemical reactions, or based on the property of the framework materials as support material.
  • the object is achieved by a method for producing a porous organometallic framework comprising the step
  • reaction can take place with stirring, which is also advantageous in a scale-up.
  • the reaction takes place at a pressure of at most 2 bar (absolute). However, the pressure is preferably at most 1230 mbar (absolute). Most preferably, the reaction takes place at atmospheric pressure.
  • the reaction can be carried out at room temperature. Preferably, however, this takes place at temperatures above room temperature. Preferably, the temperature is more than 100 ° C. Further preferably, the temperature is at most 180 ° C, and more preferably at most 150 ° C.
  • the organometallic frameworks described above are carried out in water as a solvent with the addition of another base.
  • another base serves in particular to the fact that when using a polybasic carboxylic acid as at least bidentate organic compound, this is readily soluble in water.
  • the solvent for the process according to the invention can be chosen such that it reacts basicly, - A -
  • a base can be used. However, it is preferred that no additional base is used.
  • the metal compound used for the preparation of the porous organometallic framework material may be nonionic and / or the counterion to the metal cation may be derived from a protic solvent.
  • a non-ionic compound can be avoided with a suitable choice that in the implementation of the porous organometallic framework material, the metal is present in the form of a salt and thereby possibly difficulties in the removal of the corresponding anion in the metal salt, if provided by the metal compound in the Implementation no further interfering salts are generated.
  • the counterion represents a solvent anion, this may, with suitable choice after conversion, be present as a solvent which may be the same as or different from the nonaqueous organic solvent used.
  • this solvent is at least partially miscible with the non-aqueous organic solvent. If water should form during the reaction of the metal compound, its proportion should be within the limits described below. This can be achieved by using a sufficient amount of the nonaqueous organic solvent.
  • nonionic compounds or counterions to the metal cation which can be derived from protic solvents can be, for example, metal alcoholates, for example methanolates, ethanolates, propanolates, butanolates.
  • metal alcoholates for example methanolates, ethanolates, propanolates, butanolates.
  • oxides or hydroxides are conceivable.
  • the metal used is Sc '", Y 1 " or a trivalent lanthanide.
  • the metals used can also be used as mixtures.
  • the at least one at least bidentate organic compound has at least two atoms, each of which is independently selected from the group consisting of oxygen, sulfur and nitrogen, via which the organic compound can coordinate to the metal. These atoms may be part of the skeleton of the organic compound or functional groups.
  • Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: OH, SH, NH 2 , NH (-RH), N (RH) 2 , CH 2 OH, CH 2 SH, CH 2 NH 2 , CH 2 NH (-RH), CH 2 N (-RH) 2 , -CO 2 H, COSH, -CS 2 H, -NO 2 , -B (OH) 2 , -SO 3 H, -Si (OH) 3 , -Ge (OH) 3 , -Sn (OH) 3 , -Si (SH) 4 , -Ge (SH) 4 , -Sn (SH) 3 , -PO 3 H 2 , -AsO 3 H, -AsO 4 H, -P (SH) 3 , -As (SH) 3 , -CH (RSH) 2 , -C (RSH) 3 , -CH
  • functional groups are to be mentioned in which the abovementioned radical R is absent.
  • -CH (SH) 2 , -C (SH) 3 -CH (NH 2 ) 2 , CH (NH (RH)) 2 , CH (N (R-H) 2 J 2 , C (NH (RH)) 3 , C (N (RH) 2 ) 3 , -C (NH 2 J 3 , -CH (OH) 2 , -C (OH) 3 , -CH (CN) 2 , -C (CN) 3 to call.
  • the at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinative bond and the preparation of the framework.
  • the organic compounds containing the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or an aliphatic as well as an aromatic compound.
  • the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compounds contains 1 to 18, more preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 1 1 and especially preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores may be separated from each other and / or at least two nuclei in condensed form.
  • the aromatic compound or the aromatic part of the both aliphatic and aromatic compound one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the compound mentioned may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, preferably N, O and / or S.
  • the aromatic compound or the aromatic moiety of the both aromatic and aliphatic compounds contains one or two C 6 cores, the two being either separately or in condensed form.
  • Benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may in particular be mentioned as aromatic compounds.
  • the at least bidentate organic compound is particularly preferably derived from a di-, tri- or tetracarboxylic acid or its sulfur analogs.
  • the term "derive" in the context of the present invention means that the at least bidentate organic compound can be present in the framework material in partially deprotonated or completely deprotonated form. Furthermore, the at least bidentate organic compound may contain further substituents, such as -OH, -NH 2 , -OCH 3 , -CH 3 , -NH (CH 3 ), -N (CH 3 J 2 , -CN and halides.
  • the at least bidentate organic compound is an aliphatic or aromatic acyclic or cyclic hydrocarbon having 1 to 18 carbon atoms, which moreover has exclusively at least two carboxy groups as functional groups.
  • dicarboxylic acids such as
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
  • Suitable heteroatoms are, for example, N, O, S, B, P. Preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.
  • acetylenedicarboxylic acid ADC
  • campherdicarboxylic acid fumaric acid, succinic acid
  • benzenedicarboxylic acids naphthalenedicarboxylic acids
  • biphenyldicarboxylic acids such as for example, 4,4'-biphenyldicarboxylic acid (BPDC)
  • BPDC 4,4'-biphenyldicarboxylic acid
  • pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid
  • bipyridinedicarboxylic acids such as, for example, 2,2'-bipyridine dicarboxylic acids, for example 2,2'-bipyridine-5,5'-dicarboxylic acid
  • benzenetricarboxylic acids for example 1, 2,3-, 1, 2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC)
  • the organometallic framework material may also comprise one or more monodentate ligands.
  • the at least one at least bidentate organic compound preferably contains no boron or phosphorus atoms.
  • the framework of the organometallic framework material contains no boron or phosphorus atoms.
  • the non-aqueous organic solvent is preferably a Ci -6 alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, optionally halogenated Ci -2 oo-alkane, sulfolane, glycol, N-methylpyrrolidone (NMP), gamma-butyrolactone, alicyclic alcohols such as cyclohexanol, ketones such as Acetone or acetylacetone, cycloketones, such as cyclohexanone, sulfolene or mixtures thereof.
  • DMSO dimethyl sulfoxide
  • DMF di
  • a d- 6- alkanol refers to an alcohol having 1 to 6 carbon atoms. Examples of these are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol and mixtures thereof.
  • An optionally halogenated denotes an alkane having 1 to 200 carbon atoms, it being possible for one or more up to all hydrogen atoms to be replaced by halogen, preferably chlorine or fluorine, in particular chlorine.
  • halogen preferably chlorine or fluorine, in particular chlorine.
  • chloroform preferably chloromethane, carbon tetrachloride, dichloroethane, hexane, heptane, octane and mixtures thereof.
  • Preferred solvents are DMF, DEF and NMP. Particularly preferred is DMF.
  • non-aqueous preferably refers to a solvent having a maximum water content of 10% by weight, more preferably 5% by weight, still more preferably 1% by weight, still preferably 0.1% by weight. -%, particularly preferably 0.01 wt .-%, based on the total weight of the solvent does not exceed.
  • the maximum water content during the reaction is 10% by weight, more preferably 5% by weight, and still more preferably 1% by weight.
  • solvent refers to pure solvents as well as mixtures of different solvents.
  • the step of reacting the at least one metal compound with the at least one at least bidentate organic compound is followed by a calcination step.
  • the temperature set here is typically more than 250 ° C, preferably 300 to 400 ° C.
  • the at least bidentate organic compound present in the pores can be removed.
  • the removal of the at least bidentate organic compound (ligand) from the pores of the porous organometallic framework material by the treatment of the resulting framework material with a non-aqueous solvent can be carried out.
  • the ligand is removed in a kind of "extraction process” and optionally replaced in the framework by a solvent molecule. This gentle method is particularly suitable when the ligand is a high-boiling compound.
  • the treatment is preferably at least 30 minutes and may typically be carried out for up to 2 days. This can be done at room temperature or elevated temperature. This is preferably carried out at elevated temperature, for example at at least 40 ° C., preferably 60 ° C. Further preferably, the extraction takes place at the boiling point of the solvent used instead (under reflux).
  • the treatment can be carried out in a simple boiler by slurrying and stirring the framework material. It is also possible to use extraction apparatuses such as Soxhlet apparatuses, in particular technical extraction apparatuses.
  • suitable solvents the above-mentioned can be used, for example, d-6-alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, toluene, dioxane, benzene, chlorobenzene Methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, optionally halogenated d-ooalkane, sulfolane, glycol, N-methylpyrrolidone (NMP), gamma-butyrolactone, alicyclic alcohols such as cyclohexanol, ketones,
  • a most preferred extraction solvent is methanol.
  • the solvent used for the extraction may be the same as or different from that for the reaction of the at least one metal compound with the at least one at least bidentate organic compound.
  • the solvent is anhydrous.
  • the organometallic frameworks according to the present invention contain pores, in particular micropores and / or mesopores.
  • Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as defined by Pure Applied Chem. 45, page 71, in particular on page 79 (FIG. 1976).
  • the presence of micro- and / or mesopores can be checked with the aid of sorption measurements, these measurements determining the uptake capacity of the MOF for nitrogen at 77 Kelvin according to DIN 66131 and / or DIN 66134.
  • the organometallic framework materials produced by the process according to the invention differ in that they have a comparatively low specific surface area and are nevertheless very suitable for hydrogen storage. Therefore, preferably the specific surface area of the organometallic framework materials according to the invention in powder form is less than 300 m 2 / g according to Langmuir (N 2 ) according to DIN 66135 (DIN 66131, 66134). More preferably, the specific surface area is less than 250 m 2 / g, more preferably less than 200 m 2 / g, further preferably less than 150 m 2 / g, and most preferably less than 100 m 2 / g.
  • the specific surface area is preferably at least 10 m 2 / g, more preferably at least 30 m 2 / g.
  • Framework materials that are present as shaped bodies can have a lower specific surface area.
  • the organometallic framework material can be present in powder form or as agglomerate.
  • the framework material may be used as such or it may be converted into a shaped body. Accordingly, another aspect of the present invention is a molded article containing a framework material according to the invention.
  • the framework material may include other materials such as binders, lubricants, or other additives added during manufacture. It is also conceivable that the framework material has further constituents, such as absorbents such as activated carbon or the like.
  • pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
  • Tabletting together with at least one binder and / or other excipient are provided.
  • Kneading / mulling and shaping can be carried out according to any suitable method, as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, volume 2, p. 313 et seq. (1972).
  • the kneading / hulling and / or shaping by means of a reciprocating press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, co-extruding, foaming, spinning, coating, granulation, preferably spray granulation, spraying, spray drying or a combination of two or more of these methods.
  • pellets and / or tablets are produced.
  • Kneading and / or molding may be carried out at elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.
  • elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.
  • binders for the purposes of the present invention may be both viscosity-increasing and viscosity-reducing compounds.
  • Preferred binders include, for example, alumina-containing or alumina-containing binders, as described, for example, in WO 94/29408, silica, as described, for example, in EP 0 592 050 A1, mixtures of silica and alumina, such as For example, in WO 94/13584, clay minerals, as described for example in JP 03-037156 A, for example, montmorillonite, kaolin, bentonite, halloysite, dickite, nacrit and anauxite, alkoxysilanes, as described for example in EP 0 102 544 B1, for example tetraalkoxysilanes such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane or, for example, trialkoxysilanes such as trimethoxysilane, triethoxysilane, trip
  • an organic compound and / or a hydrophilic polymer such as cellulose or a CeIIU losederivat such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran and / or a polyethylene oxide.
  • a pasting agent inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably a water-miscible polyhydric alcohol, alone or in admixture with water and / or at least one of said monohydric alcohols are used.
  • a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glyco
  • the order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.
  • the molded article obtained according to kneading and / or shaping is subjected to at least one drying, which is generally carried out at a temperature in the range from 25 to 500 ° C., preferably in the range from 50 to 500 ° C. and more preferably in Range is carried out from 100 to 350 ° C. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying. According to a particularly preferred embodiment, as part of this drying process, at least one of the compounds added as additives is at least partially removed from the shaped body.
  • Another object of the present invention is a porous organometallic framework, obtainable from a process according to the invention for its preparation.
  • the framework material preferably has the specific surfaces (according to Langmuir) specified above.
  • Another object of the present invention is the use of a porous organometallic framework according to the invention for receiving at least one substance for its storage, separation, controlled release or chemical reaction and as a carrier, for example for metals, metal oxides, metal sulfides or other framework structures.
  • porous organometallic framework according to the invention is used for storage, this is preferably carried out in a temperature range from -200 ° C to +80 ° C. More preferred is a temperature range of -40 ° C to + 80 ° C.
  • the at least one substance may be a gas or a liquid.
  • the substance is a gas.
  • gas and liquid are used in a simplified manner, but here too gas mixtures and mixtures of liquids or liquid solutions are to be understood by the term “gas” or "liquid”.
  • Preferred gases are hydrogen, natural gas, town gas, hydrocarbons, in particular methane, ethane, ethyne, acetylene, propane, n-butane and also i-butane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halide hydrocarbons, NF 3 , SF 6 , Ammonia, boranes, phosphines, hydrogen sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
  • the at least one substance may also be a liquid.
  • a liquid examples of such a liquid are disinfectants, inorganic or organic solvents, fuels - especially gasoline or diesel -, hydraulic, radiator, brake fluid or an oil, especially machine oil.
  • the liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof.
  • the at least one substance may be an odorant.
  • the odorant is a volatile organic or inorganic compound containing at least one of nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine or an unsaturated or aromatic hydrocarbon or a saturated or unsaturated aldehyde or a Ketone is. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; especially preferred are nitrogen, oxygen, phosphorus and sulfur.
  • the odorant is ammonia, hydrogen sulfide, sulfur oxides, nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and aldehydes, ketones, esters, ethers, acids or alcohols.
  • ammonia hydrogen sulphide
  • organic acids preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, lauric acid, pelargonic acid
  • cyclic or acyclic hydrocarbons which contain nitrogen or sulfur and saturated or unsaturated aldehydes, such as hexanal, heptanal, octanal, nonanal, decanal, octenal or notenal and in particular volatile aldehydes such as butyraldehyde, propionaldehyde, acetaldehyde and formaldehyde and also fuels such as gasoline, diesel (ingredients).
  • the odorous substances may also be fragrances which are used, for example, for the production of perfumes.
  • fragrances or oils which release such fragrances include: essential oils, basil oil, geranium oil, mint oil, cananga oil, cardamom oil, lavender oil, peppermint oil, nutmeg oil, chamomile oil, eucalyptus oil, rosemary oil, lemon oil, lime oil, orange oil, bergamot oil , Clary sage oil, coriander oil, cypress oil, 1, 1-dimethoxy-2-pherylethane, 2,4-dimethyl-4-phenyltetrahydrofuran, dimethyltetrahydrobenzaldehyde, 2,6-dimethyl-7-octene-2-ol, 1, 2-diethoxy-3 , 7-dimethyl-2,6-octadiene, phenylacetaldehyde, rose oxide, ethyl 2-methylpentanoate, 1- (2,6,6-trimethyl-1,
  • a volatile odorant preferably has a boiling point or boiling point range of less than 300 ° C. More preferably, the odorant is a volatile compound or mixture. Most preferably, the odorant has a boiling point or boiling range of less than 250 ° C, more preferably less than 230 ° C, most preferably less than 200 ° C.
  • odors which have a high volatility.
  • a volatile odorant preferably has a vapor pressure greater than 0.001 kPa (20 ° C). More preferably, the odorant is a volatile compound or mixture. Most preferably, the odorant has a vapor pressure of greater than 0.01 kPa (20 ° C), more preferably a vapor pressure greater than 0.05 kPa (20 ° C). Most preferably, the odors have a vapor pressure of greater than 0.1 kPa (20 ° C).
  • the reaction mixture is 48 h at 220 ° C under autogenous pressure in a Berghof autoclave ("Teflon liner”) left.
  • the filter cake is washed with 20 ml of H 2 O and twice with 20 ml of ethanol.
  • the yellow residue is suspended in 80 ml of EtOH and sonicated for two hours.
  • the solid is washed twice with 50 ml of ethanol and dried in a vacuum oven at 140 ° C for 72 h.
  • the unevenly yellow-colored solid is calcined in a drying oven for 48 h at 290 ° C (air flow 100 l / h). This gives 2.33 g of a pale yellow colored solid.
  • the diffractogram is shown in Fig. 3.
  • the framework material has 366 m 2 / g (Langmuir evaluation). Elemental analysis shows 20.6 wt% Sc and 41.6 wt% carbon.
  • MOF-5 is known to those skilled in the art as a suitable framework for H 2 storage at 77K.
  • a suitable method of synthesis is disclosed, for example, in WO-A 03/102000.
  • the material has in the surface determination with N 2 a value of 2740 m 2 / g (Langmuir).
  • the diffractogram is shown in Fig. 4.
  • the framework material shows in the surface determination with N 2 only 83 m 2 / g (Langmuir evaluation). Elemental analysis shows 26.6 wt% yttrium and 42.5 wt% carbon.
  • Fig. 1 shows the comparison of H 2 uptake for three materials.
  • the framework material has only 49 m 2 / g in the surface determination with N 2 (Langmuir evaluation).
  • the elemental analysis shows 31, 0 wt% Gd, 24.8 wt% C, 12.7 wt% N and 2.2 wt% H.
  • the framework material has a new crystalline MOF structure in the diffractogram.
  • the framework material has only 41 m 2 / g in the surface determination with N 2 (Langmuir evaluation).
  • the elemental analysis shows 30.0 wt% Sm, 25.7 wt% C, 13.3 wt% N and 2.3 wt% H.
  • the framework material has a new crystalline MOF structure in the diffractogram.
  • the framework material has only 28 m 2 / g in the surface determination with N 2 (Langmuir evaluation).
  • the framework material has a new crystalline MOF structure in the diffractogram.

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Abstract

La présente invention concerne un procédé de fabrication d'un matériau structurel poreux métallo-organique, comprenant une étape de réaction d'au moins un composé métallique avec au moins un composé organique au moins bidentate pouvant se coordonner au métal, en présence d'un solvant organique non aqueux, ledit métal étant Sc<SUP>III</SUP>, Y<SUP>III </SUP>ou un lanthanide trivalent, et ledit composé organique comportant au moins deux atomes, choisis chacun indépendamment parmi l'oxygène, le soufre et l'azote, par lesquels le composé organique peut se coordonner au métal, ladite réaction étant réalisée sous agitation et à une pression (absolue) d'au maximum 2 bars. L'invention concerne également les matériaux structurels poreux métallo-organiques obtenus par ce procédé, ainsi que leur utilisation.
EP06819465A 2005-11-16 2006-11-14 Materiaux structurels metallo-organiques du sous-groupe iii Withdrawn EP1954395A1 (fr)

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DE102005054636A DE102005054636A1 (de) 2005-11-16 2005-11-16 Metallorganische Gerüstmaterialien der III. Nebengruppe
PCT/EP2006/068446 WO2007057391A1 (fr) 2005-11-16 2006-11-14 Materiaux structurels metallo-organiques du sous-groupe iii

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Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
DE112007001530A5 (de) * 2006-06-26 2009-05-14 Basf Se Speicherung von acetylenhaltigen Gasen mit Hilfe von metallorganischen Gerüstmaterialien
KR20100016188A (ko) * 2007-04-05 2010-02-12 바스프 에스이 금속 유기 골격 성분 및 잠열 저장 성분을 포함하는 혼합물을 포함하는 가스 압력 용기
US8372779B2 (en) * 2007-04-24 2013-02-12 Basf Se Metal organic frameworks based on aluminum, iron and chromium
TW200914115A (en) * 2007-05-14 2009-04-01 Shell Int Research Process for producing purified natural gas from natural gas comprising water and carbon dioxide
US8313559B2 (en) * 2007-05-21 2012-11-20 Basf Se Aluminum aminocarboxylates as porous metal organic frameworks
WO2008142093A1 (fr) * 2007-05-24 2008-11-27 Basf Se Composition de polissage chimico-mécanique contenant des matières structurantes organométalliques
EP2176201B1 (fr) * 2007-07-10 2014-06-04 Basf Se Procédé de séparation d'hydrocarbures non ramifiés de leurs isomères ramifiés
WO2009034048A1 (fr) 2007-09-10 2009-03-19 Shell Internationale Research Maatschappij B.V. Procédé de production, au moyen d'une structure métallo-organique, de gaz de synthèse purifié à partir de gaz de synthèse contenant des traces de contaminants soufrés
CN101935277B (zh) * 2009-06-29 2013-12-25 深圳市普迈达科技有限公司 多孔稀土金属有机骨架材料、其制备方法及其于天然气储存的应用
US8425662B2 (en) 2010-04-02 2013-04-23 Battelle Memorial Institute Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies
GB201207208D0 (en) * 2012-04-25 2012-06-06 Johnson Matthey Plc Compound and method of manufacture
CN103933939A (zh) * 2014-04-09 2014-07-23 同济大学 一种高甲烷吸附存储密度的金属-有机骨架mof材料
CN107746465B (zh) * 2017-10-01 2020-10-23 桂林理工大学 一种以3，5-吡唑二羧酸为配体构筑的Nd-MOF材料及制备方法
CN108164715B (zh) * 2018-02-08 2020-06-09 中国科学院福建物质结构研究所 一种稀土有机框架晶体材料、其制备方法及应用
CN112625255B (zh) * 2019-11-28 2022-02-01 福建农林大学 一种定量检测次氯酸根离子的比例型荧光探针的合成方法与应用
CN111909028B (zh) * 2020-08-24 2022-11-29 北京石油化工学院 一种用于检测AFB1的Eu/Tb(BTC)的制备方法
CN114478970B (zh) * 2020-10-26 2023-11-03 中国科学院大连化学物理研究所 一种共价有机骨架材料的前驱体组合物及其应用
CN114773616B (zh) * 2022-04-29 2023-07-14 南开大学 分子印迹混合配体镧系三金属-有机框架及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5648508A (en) * 1995-11-22 1997-07-15 Nalco Chemical Company Crystalline metal-organic microporous materials
DE10111230A1 (de) * 2001-03-08 2002-09-19 Basf Ag Metallorganische Gerüstmaterialien und Verfahren zu deren Herstellung
ATE334992T1 (de) * 2001-04-30 2006-08-15 Univ Michigan Isoretikuläre organometallische grundstrukturen, verfahren zu deren bildung und systematische entwicklung von deren porengrösse und funktionalität, mit anwendung für die gasspeicherung

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BARRERA A ET AL: "Radial distribution function studies of Al2O3-La2O3 binary oxides prepared by sol-gel", CATALYSIS COMMUNICATIONS, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 5, no. 10, 1 October 2004 (2004-10-01), pages 569 - 574, XP027080690, ISSN: 1566-7367, [retrieved on 20040915], DOI: 10.1016/J.CATCOM.2004.07.007 *
PITOIS C ET AL: "Lanthanide-cored fluorinated dendrimer complexes: synthesis and luminescence characterization", JOURNAL OF LUMINESCENCE, ELSEVIER BV NORTH-HOLLAND, NL, vol. 111, no. 4, 1 March 2005 (2005-03-01), pages 265 - 283, XP027659748, ISSN: 0022-2313, [retrieved on 20050301] *
See also references of WO2007057391A1 *
WANG J ET AL: "Synthesis, reactivity and structural characterization of linked bis(amidinate) ytterbium complexes", JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER, AMSTERDAM, NL, vol. 743, no. 1-3, 31 May 2005 (2005-05-31), pages 229 - 235, XP027660035, ISSN: 0022-2860, [retrieved on 20050531] *

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DE102005054636A1 (de) 2007-05-24
JP2009515930A (ja) 2009-04-16
CA2630035A1 (fr) 2007-05-24
US20080300387A1 (en) 2008-12-04

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