EP2010315A2 - Organometallic aluminum fumarate backbone material - Google Patents

Organometallic aluminum fumarate backbone material

Info

Publication number
EP2010315A2
EP2010315A2 EP07728034A EP07728034A EP2010315A2 EP 2010315 A2 EP2010315 A2 EP 2010315A2 EP 07728034 A EP07728034 A EP 07728034A EP 07728034 A EP07728034 A EP 07728034A EP 2010315 A2 EP2010315 A2 EP 2010315A2
Authority
EP
European Patent Office
Prior art keywords
framework
substance
porous organometallic
framework material
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07728034A
Other languages
German (de)
French (fr)
Inventor
Christoph Kiener
Ulrich Mueller
Markus Schubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07728034A priority Critical patent/EP2010315A2/en
Publication of EP2010315A2 publication Critical patent/EP2010315A2/en
Ceased legal-status Critical Current

Links

Classifications

    • 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 System
    • C07F5/06—Aluminium compounds
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 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
    • 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
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J31/2226—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
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • 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
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/15—Fumaric acid
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • 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
    • B01J2531/31—Aluminium
    • 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
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]

Definitions

  • the present invention relates to a porous organometallic framework material, moldings containing it, to processes for the preparation of the framework material and to its use.
  • Porous organometallic frameworks are known in the art. They are characterized in particular by their porosity and are often fed comparable applications, which are known of inorganic zeolites.
  • Organometallic frameworks usually contain a coordinated to a metal ion, at least bidentate organic compound, which represents together with the metal ion, the backbone of the organometallic framework.
  • the appropriate choice of metal and / or organic compound allows optimization for the desired field of application.
  • the choice of organic compound can influence the pore distribution.
  • the metal can contribute to adsorption processes.
  • Aluminum can be mentioned as an interesting metal since, owing to strong coordination bonds, comparatively robust organometallic framework materials can be obtained. In addition, due to its octaetric coordination, the aluminum ion is in principle suitable for building up three-dimensional framework connections. Furthermore, the salts of aluminum used as starting materials are easily accessible and inexpensive.
  • the object is achieved by a porous organometallic framework material formed from Al '"ions to which coordinative fumarations are bonded to form a framework structure. It has been found that the porous organometallic framework material formed from aluminum ions and fumarations (trans-1, 2-ethylene dicarboxylate) surprisingly has a one-dimensional channel structure, which also shows a surprisingly high specific surface area, so that the organometallic framework material of the present invention is particularly suitable for the Storage and separation of chemical substances, especially gases, may be.
  • the porous organometallic framework according to the invention is thus characterized by a one-dimensional channel structure, which is formed as an orthorhombic structure.
  • the structure of the porous organometallic framework according to the invention can be recognized in particular by the fact that the X-ray diffractiongram (XRD) has a base reflection in the range of 8 ° ⁇ 2 ⁇ ⁇ 12 °.
  • XRD X-ray diffractiongram
  • Fig. 1 the X-ray diffractogram of the porous organometallic framework according to the invention is shown.
  • the intensity I (Lin (counts)) is shown as a function of the 2 theta scale (2 ⁇ ).
  • the diffractogram can be determined as follows: The sample is incorporated as a powder into the sample container of a commercially available device (Siemens D-5000 diffractometer or Bruker D8-Advance).
  • the radiation source used is Cu-K ⁇ radiation with variable primary and secondary apertures and secondary monochromator.
  • the signal is detected by a scintillation (Siemens) or Solex semiconductor detector (Bruker).
  • the measuring range for 2 ⁇ is typically chosen between 2 ° and 70 °.
  • the angular step is 0.02 °, the measuring time per angular step typically 2 to 4 seconds.
  • a surface analysis can be done manually by applying a baseline to the individual reflections.
  • programs such as "Topas profiles" from Bruker can be used, the background adaptation then preferably being carried out automatically via a polynomial of the first degree in the software.
  • the structure of the framework material according to the invention has a one-dimensional channel structure in which linear chains of Al "ions and OH groups are bridged via the organic fumarate to form a three-dimensional, orthorhombic structure.
  • the organometallic framework according to the invention can be present in powder form or as an agglomerate.
  • the porous organometallic framework according to the invention can be used as such in powder form or it is converted into a shaped body.
  • porous organometallic framework of the present invention is a powder.
  • a further aspect of the present invention is accordingly a shaped body containing the porous organometallic framework 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.
  • 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 may be both viscosity-increasing and viscosity-reducing compounds.
  • Preferred binders include, for example, alumina or alumina-containing binders such as those described in WO 94/29408, silica such as described in EP 0 592 050 A1, mixtures of silica and alumina, such as those described in U.S.
  • an organic compound and / or a hydrophilic polymer such as cellulose or a CeIIU losederivat such as methyl cellulose 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 are used.
  • 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 glycol, preferably
  • 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 molding obtained according to kneading and / or molding is subjected to at least one drying, generally at a temperature in the range of 25 to 500 ° C, preferably in the range of 50 to 500 ° C and more preferably in the range of 100 to 350 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
  • At least one of the compounds added as additives is at least partially removed from the shaped body.
  • the organometallic framework according to the invention contains 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 (Pure & Appl. Chem. 57 (1985) 603-619).
  • the presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the uptake capacity of the organometallic frameworks for nitrogen at 77 Kelvin (according to Langmuir) according to DIN 66131 and / or DIN 66134.
  • the pores are in the form of one-dimensional channels having a diameter of 5 to 15 angstroms, more preferably 7 to 12 ⁇ .
  • the specific surface area - calculated according to the Langmuir model (DIN 66131, 66134) for the organometallic framework according to the invention in powder form is at least 1000 m 2 / g, more preferably at least 1200 m 2 / g, more preferably at least 1400 m 2 / g, more preferably at least 1600 m 2 / g, more preferably at least 1800 m 2 / g and particularly preferably at least 1950 m 2 / g.
  • Shaped bodies of the organometallic framework according to the invention may have a lower specific surface; but preferably at least 500 m 2 / g, more preferably at least 600 m 2 / g, even more preferably at least 700 m 2 / g, in particular at least 800 m 2 / g.
  • Another object of the present invention is a method for producing a porous organometallic framework according to the invention, comprising the step Reaction of a reaction mixture comprising at least one aluminum compound and fumaric acid or a salt thereof in the presence of an organic solvent at a predetermined temperature and a predetermined pressure.
  • the organic component of the porous organometallic framework of the invention is fumaric acid, which can be reacted with an aluminum compound. It is also possible to use derivatives of fumaric acid. For example, it is conceivable that fumaric acid is used in the form of its salt.
  • the salt in which fumaric acid is present as a fully or partially deprotonated anion may have any suitable cation.
  • Such cations may be, for example, mono- or divalent, preferably monovalent metal ions. Examples of these are in particular sodium and potassium salts. Likewise, cations of ammonium compounds can be used. In particular, ammonium itself and alkylammonium cations should be mentioned here.
  • the aluminum compound can be produced by anodic oxidation of metallic aluminum.
  • the porous organometallic framework according to the invention is prepared at least partially by electrochemical means. Methods for the electrochemical preparation of porous organometallic frameworks are described in WO-A 2005/049892. The production of the aluminum compound for the porous organometallic framework according to the invention can also be prepared in this way.
  • the cathodic redeposition of the aluminum ion is at least partially prevented by at least one of the following measures:
  • the process can be carried out in an undivided electrolysis cell.
  • Especially suitable cells are split cells or plate-stack cells. These can be switched bipolar.
  • As a reaction medium for example, methanol, ethanol, di- methylformamide, diethylformamide or a mixture of two or more of these solvents.
  • a conductive salt or a plurality of conductive salts may furthermore be present.
  • the conductive salt can have a quaternary ammonium as the cation component and an alkoxy sulfate as the anion component.
  • the total solids content should be in the range of greater than or equal to 0.5% by weight.
  • the reaction in the process according to the invention for the preparation of the organometallic framework according to the invention can also be carried out by conventional means.
  • the aluminum compound is typically an aluminum salt.
  • the aluminum salt may be in the form of an alcoholate, acetonate, halegonide, sulfite, salt of an organic or inorganic oxygen-containing acid, or a mixture thereof.
  • An alcoholate is, for example, a methoxide, ethanolate, n-propoxide, i-propanolate, n-butoxide, i-butoxide, t-butoxide or phenolate.
  • An acetonate is, for example, acetylacetonate.
  • a halide is, for example, chloride, bromide or iodide.
  • An organic, oxygen-containing acid is, for example, formic acid, acetic acid, propionic acid or other alkyl monocarboxylic acids.
  • An inorganic, oxygen-containing acid is, for example, sulfuric acid, sulfurous acid, phosphoric acid or nitric acid.
  • Aluminum compounds are inorganic aluminum salts such as aluminum chloride, aluminum bromide, aluminum hydrogen sulfate, aluminum dihydrogen phosphate, aluminum monohydrogen phosphate, aluminum phosphate, aluminum nitrate.
  • the aluminum compound may optionally have water of hydration, which is preferable.
  • the hydrates of the chloride, nitrate and sulfate are particularly preferred as the aluminum compound.
  • reaction in the process according to the invention for the preparation of the porous organometallic framework according to the invention takes place at least in the presence an organic solvent.
  • Solvothermal conditions can be used here.
  • thermal is to be understood as meaning a preparation process in which the conversion to the porous organometallic framework according to the invention is carried out in a pressure vessel such that it is closed during the reaction and elevated temperature is applied, so that due to the vapor pressure of existing solvent, a pressure builds up within the reaction medium in the pressure vessel.
  • the reaction does not occur in water-containing medium and also not under solvothermal conditions.
  • reaction in the process according to the invention is therefore preferably carried out in the presence of a non-aqueous solvent.
  • the reaction is preferably carried out at a pressure of 1 bar to 16 bar (absolute), preferably 1 to 3 bar (absolute). More preferably, however, the pressure is at most 1230 mbar (absolute). Particularly preferably, the reaction takes place at atmospheric pressure. However, this may lead to slight overpressure or depression due to the apparatus. Therefore, in the context of the present invention, the term "atmospheric pressure" is to be understood as the pressure range which results from the actual atmospheric pressure of ⁇ 150 mbar.
  • the reaction preferably takes place in a temperature range from 100.degree. C. to 200.degree.
  • the temperature is in the range of 1 10 ° C to 170 ° C.
  • the temperature is in a range of 120 ° C to 150 ° C.
  • the reaction mixture may further comprise a base.
  • a base serves, in particular, that when the carboxylic acid is used as the at least bidentate organic compound, it is readily soluble.
  • an organic solvent it is often not necessary to use such a base.
  • the solvent for the process according to the invention can be chosen such that it reacts basicly as such, but this does not necessarily have to be for carrying out the process according to the invention.
  • a base can be used. However, it is preferred that no additional base is used. It is also advantageous that the reaction can take place with stirring, which is also advantageous in a scale-up.
  • the (non-aqueous) organic solvent is preferably a d-6-alkanol, dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc) , Acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, optionally halogenated d, ooalkane, sulfolane, glycol, N-methylpyrrolidone (NMP), glycerol.
  • DMSO dimethylsulfoxide
  • DMF N-dimethylformamide
  • DEF N-diethylformamide
  • DMAc N-dimethylacetamide
  • ma-butyrolactone alicyclic alcohols such as cyclohexanol, ketones such as acetone or acetylacetone, cycloketones such as cyclohexanone, sulfolene or mixtures thereof.
  • a C- ⁇ - 6- alkanol denotes an alcohol having 1 to 6 C 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, where one or more up to all hydrogen atoms may be replaced by halogen, preferably chlorine or fluorine, in particular chlorine, or may be. Examples thereof are chloroform, dichloromethane, tetrachloromethane, dichloroethane, hexane, heptane, octane and mixtures thereof.
  • Preferred solvents are DMF, DEF, DMAc 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, further 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 process 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. Due to the calcination step, 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.
  • the treatment is preferably at least 30 minutes and may typically be carried out for up to 7 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 of (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.
  • the above-mentioned can be used, that is, for example, d-6-alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), acetic acid ethyl ester, 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 or mixture
  • 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. It is not essential in the "extraction” but preferred that the solvent is anhydrous. It is preferred that in the process according to the invention the molar ratio of aluminum compound to fumaric acid or one of its salts is in the range of 0.3: 1 to 1.7: 1. More preferably, the ratio is in the range of 0.7: 1 to 1.2: 1.
  • 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, chemical reaction or as a carrier.
  • the at least one substance is a gas or gas mixture. Also liquids are possible.
  • organometallic frameworks Methods for storage with the aid of organometallic frameworks in general are described in WO-A 2005/003622, WO-A 2003/064030, WO-A 2005/049484, WO-A 2006/089908 and DE-A 10 2005 012 087.
  • the processes described there can also be used for the organometallic framework according to the invention.
  • Preferred gases for storage are methane or hydrogen.
  • a preferred gas to be separated off is carbon dioxide, in particular from a gas mixture which furthermore contains carbon monoxide.
  • 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.
  • a preferred pressure range is 20 bar to 1000 bar (absolute), in particular 100 bar to 400 bar.
  • 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, ethene, acetylene, propane, n-butane and also i-butane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halogenated carbon atoms.
  • the gas is carbon dioxide which is separated from a gas mixture containing carbon dioxide.
  • the gas mixture in addition to carbon dioxide at least H 2 , CH 4 or carbon monoxide.
  • the gas mixture has carbon monoxide in addition to carbon dioxide.
  • mixtures which contain at least 10 and at most 45% by volume of carbon dioxide and at least 30 and at most 90% by volume of carbon monoxide.
  • a preferred embodiment is the pressure swing adsorption with a plurality of parallel adsorber reactors, wherein the adsorbent bulk consists wholly or partly of the material according to the invention.
  • the adsorption phase takes place for the CO 2 / CO separation preferably at a CO 2 partial pressure of 0.6 to 3 bar and a temperature of at least 20 but not more than 70 ° C.
  • the total pressure in the relevant adsorber reactor is usually lowered to values between 100 mbar and 1 bar.
  • the framework material according to the invention for storing a gas at a minimum pressure of 100 bar (absolute). More preferably, the minimum pressure is 200 bar (absolute), in particular 300 bar (absolute). These are particularly preferably in the gas to hydrogen or methane.
  • 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 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 , Muscat 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-methyl-pentanoate, 1- (2,6,6-trimethyl-1,3
  • 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 of more 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). Particularly preferably, the odorants have a vapor pressure of more than 0.1 kPa (20 ° C.).
  • organometallic framework according to the invention examples in which a chemical reaction can take place in the presence of the organometallic framework according to the invention are the alkoxylation of monools and polyols. The performance of such alkoxylations is described in WO-A 03/035717 and WO-A 2005/03069.
  • the porous organometallic framework according to the invention for epoxidation and preparation of polyalkylene and hydrogen peroxide can be used. Such reactions are described in WO-A 03/101975, WO-A 2004/037895 and US-A 2004/081611.
  • organometallic framework according to the invention can serve as a carrier, in particular as a carrier of a catalyst.
  • FIG. 2 shows the H 2 uptake of the MOF according to the invention.
  • the measurement is carried out on a commercially available device from the company Quantachrome with the designation Autosorb-1.
  • the measuring temperature is 77.4 K.
  • the sample is pretreated for 4 hours at room temperature before the measurement and then for a further 4 hours at 200 ° C. in vacuo.
  • FIG. 3 shows the H 2 uptake for the Al fumarate MOF.
  • the measurement temperature is 77.4 K.
  • the samples are each pretreated for 4 hours at room temperature and then for a further 4 hours at 200 ° C. in vacuum before the measurement.
  • the hydrogen uptake (g / l) is shown as a function of the absolute pressure p (bar).
  • absorbed amount A (mg / g) is shown as a function of the absolute pressure p (mbar). Curves 1, 2 and 3 correspond to the gases CO 2 , methane and CO.

Abstract

The invention relates to a porous organometallic backbone material that is formed by AIIII ions to which fumarate ions are bound so as to embody a backbone structure. The invention further relates to molded articles containing such a porous organometallic backbone material as well as the production and use thereof as a carrier or for absorbing a substance in order to store said substance, dispense the same in a controlled manner, separate or chemically react the same.

Description

Metallorganisches Gerüstmaterial aus AluminiumfumaratOrganometallic framework of aluminum fumarate
Beschreibungdescription
Die vorliegende Erfindung betrifft ein poröses metallorganisches Gerüstmaterial, Formkörper dieses enthaltend, Verfahren zur Herstellung des Gerüstmaterials sowie dessen Verwendung.The present invention relates to a porous organometallic framework material, moldings containing it, to processes for the preparation of the framework material and to its use.
Poröse metallorganische Gerüstmaterialien sind im Stand der Technik bekannt. Sie zeichnen sich insbesondere durch ihre Porosität aus und sind häufig vergleichbaren Anwendungen zuführbar, welche von anorganischen Zeolithen bekannt sind.Porous organometallic frameworks are known in the art. They are characterized in particular by their porosity and are often fed comparable applications, which are known of inorganic zeolites.
Metallorganische Gerüstmaterialien enthalten üblicherweise eine an ein Metallion koordinativ gebundene, mindestens zweizähnige organische Verbindung, die gemein- sam mit dem Metallion das Gerüst des metallorganischen Gerüstmaterials darstellt.Organometallic frameworks usually contain a coordinated to a metal ion, at least bidentate organic compound, which represents together with the metal ion, the backbone of the organometallic framework.
Die geeignete Wahl von Metall und/oder organischer Verbindung ermöglicht eine Optimierung für das gewünschte Anwendungsgebiet. Hierbei kann beispielsweise die Wahl der organischen Verbindung Einfluss auf die Porenverteilung nehmen. Darüber hinaus kann das Metall einen Beitrag bei Adsorptionsvorgängen liefern.The appropriate choice of metal and / or organic compound allows optimization for the desired field of application. In this case, for example, the choice of organic compound can influence the pore distribution. In addition, the metal can contribute to adsorption processes.
Es existiert also ein stetiger Bedarf, spezielle metallorganische Gerüstmaterialien bereitzustellen, die insbesondere außergewöhnliche Eigenschaften aufweisen, welche auf die Wahl des Metalls sowie der organischen Verbindung zurückzuführen sind.Thus, there is a continuing need to provide specific organometallic frameworks which, in particular, have exceptional properties due to the choice of metal as well as the organic compound.
Als ein interessantes Metall kann Aluminium genannt werden, da aufgrund starker Koordinationsbindungen vergleichsweise robuste metallorganische Gerüstmaterialien erhalten werden können. Zudem ist das Aluminiumion aufgrund seiner oktaetrischen Koordination prinzipiell geeignet, dreidimensionale Gerüstverbindungen aufzubauen. Weiterhin sind die als Einsatzstoffe verwendeten Salze des Aluminiums gut zugänglich und preiswert.Aluminum can be mentioned as an interesting metal since, owing to strong coordination bonds, comparatively robust organometallic framework materials can be obtained. In addition, due to its octaetric coordination, the aluminum ion is in principle suitable for building up three-dimensional framework connections. Furthermore, the salts of aluminum used as starting materials are easily accessible and inexpensive.
Eine Aufgabe der vorliegenden Erfindung liegt somit darin, Gerüstmaterialien auf Basis von Aluminium bereitzustellen, die besondere Eigenschaften insbesondere in Bezug auf die Speicherung und Trennung von chemischen Stoffen, wie Gasen, aufweisen.It is therefore an object of the present invention to provide aluminum-based frameworks which have particular properties, in particular with regard to the storage and separation of chemical substances, such as gases.
Die Aufgabe wird gelöst durch ein poröses metallorganisches Gerüstmaterial, gebildet aus Al'"-Ionen, an die koordinativ Fumarationen unter Ausbildung einer Gerüststruktur gebunden sind. Es wurde gefunden, dass das aus Aluminiumionen und Fumarationen (trans-1 ,2- Ethylendicarboxylat) gebildete poröse metallorganische Gerüstmaterial überraschenderweise eine eindimensionale Kanalstruktur aufweist, die zudem eine überraschend hohe spezifische Oberfläche zeigt, so dass das metallorganische Gerüstmaterial der vorliegenden Erfindung besonders geeignet für die Speicherung und Trennung von chemischen Stoffen, insbesondere Gasen, sein kann.The object is achieved by a porous organometallic framework material formed from Al '"ions to which coordinative fumarations are bonded to form a framework structure. It has been found that the porous organometallic framework material formed from aluminum ions and fumarations (trans-1, 2-ethylene dicarboxylate) surprisingly has a one-dimensional channel structure, which also shows a surprisingly high specific surface area, so that the organometallic framework material of the present invention is particularly suitable for the Storage and separation of chemical substances, especially gases, may be.
Das erfindungsgemäße poröse metallorganische Gerüstmaterial zeichnet sich somit durch eine eindimensionale Kanalstruktur aus, die als orthorhombische Struktur aus- gebildet ist.The porous organometallic framework according to the invention is thus characterized by a one-dimensional channel structure, which is formed as an orthorhombic structure.
Die Struktur des erfindungsgemäßen porösen metallorganischen Gerüstmaterials kann insbesondere daran erkannt werden, dass das Röntgendiffraktrogramm (XRD) einen Basisreflex im Bereich von 8° < 2Θ < 12° aufweist.The structure of the porous organometallic framework according to the invention can be recognized in particular by the fact that the X-ray diffractiongram (XRD) has a base reflection in the range of 8 ° <2Θ <12 °.
In Fig. 1 ist das Röntgendiffraktogramm des erfindungsgemäßen porösen metallorganischen Gerüstmaterials gezeigt. Hierbei ist die Intensität I (Lin(counts)) als Funktion der 2 Theta-Skala (2Θ) dargestellt.In Fig. 1, the X-ray diffractogram of the porous organometallic framework according to the invention is shown. Here, the intensity I (Lin (counts)) is shown as a function of the 2 theta scale (2Θ).
Hierbei kann das Diffraktogramm wie folgt ermittelt werden: Die Probe wird als Pulver in den Probenbehälter eines kommerziell erhältlichen Geräts (Siemens D-5000 Diffrak- tometer oder Bruker D8-Advance) eingebaut. Als Strahlungsquelle wird Cu-Kα- Strahlung mit variablen Primär- und Sekundärblenden und Sekundärmonochromator benutzt. Die Detektion des Signals erfolgt über einen Szintillations- (Siemens) oder Solex-Halbleiter Detektor (Bruker). Der Messbereich für 2θ wird typischerweise zwischen 2° und 70° gewählt. Der Winkelschritt beträgt 0,02°, die Messzeit pro Winkelschritt typischerweise 2 bis 4 Sekunden. Bei der Auswertung werden Reflexe durch eine wenigstens 3-fach höhere Signalstärke vom Grundrauschen unterschieden. Eine Flächenanalyse kann manuell erfolgen, indem an die einzelnen Reflexe eine Basislinie angelegt wird. Alternativ können Programme wie zum Beispiel "Topas-Profile" der Fa. Bruker eingesetzt werden, wobei die Untergrundanpassung dann bevorzugt über ein Polynom 1. Grades in der Software automatisch erfolgt.Here, the diffractogram can be determined as follows: The sample is incorporated as a powder into the sample container of a commercially available device (Siemens D-5000 diffractometer or Bruker D8-Advance). The radiation source used is Cu-Kα radiation with variable primary and secondary apertures and secondary monochromator. The signal is detected by a scintillation (Siemens) or Solex semiconductor detector (Bruker). The measuring range for 2θ is typically chosen between 2 ° and 70 °. The angular step is 0.02 °, the measuring time per angular step typically 2 to 4 seconds. In the evaluation reflexes are distinguished by a signal strength at least 3 times higher than the noise floor. A surface analysis can be done manually by applying a baseline to the individual reflections. Alternatively, programs such as "Topas profiles" from Bruker can be used, the background adaptation then preferably being carried out automatically via a polynomial of the first degree in the software.
Die Struktur des erfindungsgemäßen Gerüstmaterials weist eine eindimensionale Ka- nalstruktur auf, bei der lineare Ketten aus Al'"-Ionen und OH-Gruppen über das organische Fumarat zu einer dreidimensionalen, orthorhombischen Struktur verbrückt werden.The structure of the framework material according to the invention has a one-dimensional channel structure in which linear chains of Al "ions and OH groups are bridged via the organic fumarate to form a three-dimensional, orthorhombic structure.
Das erfindungsgemäße metallorganische Gerüstmaterial kann pulverförmig bezie- hungsweise als Agglomerat vorliegen. Das erfindungsgemäße poröse metallorganische Gerüstmaterial kann als solches in Pulverform verwendet werden oder es wird in einen Formkörper umgewandelt.The organometallic framework according to the invention can be present in powder form or as an agglomerate. The porous organometallic framework according to the invention can be used as such in powder form or it is converted into a shaped body.
Dementsprechend ist ein weiterer Aspekt der vorliegenden Erfindung, dass das erfindungsgemäße poröse metallorganische Gerüstmaterial als Pulver vorliegt.Accordingly, another aspect of the present invention is that the porous organometallic framework of the present invention is a powder.
Ein weiterer Aspekt der vorliegenden Erfindung ist demzufolge ein Formkörper enthaltend das erfindungsgemäße poröse metallorganische Gerüstmaterial.A further aspect of the present invention is accordingly a shaped body containing the porous organometallic framework according to the invention.
Die Herstellung von Formkörpern aus metallorganischen Gerüstmaterialien ist beispielsweise in WO-A 03/102000 beschrieben.The production of moldings from organometallic frameworks is described for example in WO-A 03/102000.
Bevorzugte Verfahren zur Herstellung von Formkörpern sind hierbei die Verstrangung oder Tablettierung. Bei der Formkörperherstellung kann das Gerüstmaterial weitere Materialien, wie beispielsweise Binder, Gleitmittel oder andere Additive aufweisen, welche während der Herstellung hinzugesetzt werden. Ebenso ist es denkbar, dass das Gerüstmaterial weitere Bestandteile aufweist, wie zum Beispiel Absorbentien wie Aktivkohle oder dergleichen.Preferred processes for the production of moldings are extruding or tableting. In molded article production, 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.
Hinsichtlich der möglichen Geometrien der Formkörper existieren im Wesentlichen keine Beschränkungen. Beispielsweise sind unter anderem Pellets wie beispielsweise scheibenförmige Pellets, Pillen, Kugeln, Granulat, Extrudate wie beispielsweise Stränge, Waben, Gitter oder Hohlkörper zu nennen.There are essentially no restrictions with regard to the possible geometries of the shaped bodies. For example, pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
Zur Herstellung dieser Formkörper sind grundsätzlich sämtliche geeigneten Verfahren möglich. Es sind insbesondere folgende Verfahrensführungen bevorzugt:In principle, all suitable processes are possible for producing these shaped bodies. In particular, the following procedures are preferred:
Kneten/Kollern des Gerüstmaterials allein oder zusammen mit mindestens einem Bindemittel und/oder mindestens einem Anteigungsmittel und/oder mindestens einer Templatverbindung unter Erhalt eines Gemisches; Verformen des erhaltenen Gemisches mittels mindestens einer geeigneten Methode wie beispielsweise Extrudieren; Optional Waschen und/oder Trocknen und/oder Calcinieren des Extrudates; Optional Konfektionieren.Kneading / rumbling of the framework material alone or together with at least one binder and / or at least one pasting agent and / or at least one template compound to obtain a mixture; Shaping the resulting mixture by at least one suitable method such as extrusion; Optionally washing and / or drying and / or calcining the extrudate; Optional assembly.
Tablettieren zusammen mit mindestens einem Bindemittel und/oder anderem Hilfestoff. Aufbringen des Gerüstmaterials auf mindestens ein gegebenenfalls poröses Trägermaterial. Das erhaltene Material kann dann gemäß der vorstehend beschriebenen Methode zu einem Formkörper weiterverarbeitet werden.Tabletting together with at least one binder and / or other Hilfestoff. Applying the framework material to at least one optionally porous support material. The material obtained can then be further processed according to the method described above to give a shaped body.
- Aufbringen des Gerüstmaterials auf mindestens ein gegebenenfalls poröses Substrat.- Applying the framework material on at least one optionally porous substrate.
Kneten/Kollern und Verformen kann gemäß eines jeden geeigneten Verfahrens erfolgen, wie beispielsweise in Ullmanns Enzyklopädie der Technischen Chemie, 4. Auflage, Band 2, S. 313 ff. (1972) beschrieben.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).
Beispielsweise kann das Kneten/Kollern und/oder Verformen mittels einer Kolbenpresse, Walzenpresse in Anwesenheit oder Abwesenheit mindestens eines Bindermaterials, Compoundieren, Pelletieren, Tablettieren, Extrudieren, Co-Extrudieren, Verschäumen, Verspinnen, Beschichten, Granulieren, bevorzugt Sprühgranulieren, Versprühen, Sprühtrocknen oder einer Kombination aus zwei oder mehr dieser Methoden erfolgen.For example, 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.
Ganz besonders bevorzugt werden Pellets und/oder Tabletten hergestellt.Most preferably, pellets and / or tablets are produced.
Das Kneten und/oder Verformen kann bei erhöhten Temperaturen wie beispielsweise im Bereich von Raumtemperatur bis 300°C und/oder bei erhöhtem Druck wie beispielsweise im Bereich von Normaldruck bis hin zu einigen hundert bar und/oder in einer Schutzgasatmosphäre wie beispielsweise in Anwesenheit mindestens eines Edelgases, Stickstoff oder einem Gemisch aus zwei oder mehr davon erfolgen.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.
Das Kneten und/oder Verformen wird gemäß einer weiteren Ausführungsform unter Zugabe mindestens eines Bindemittels durchgeführt, wobei als Bindemittel grundsätzlich jede chemische Verbindung eingesetzt werden kann, die die zum Kneten und/oder Verformen gewünschte Viskosität der zu verknetenden und/oder verformenden Masse gewährleistet. Demgemäß können Bindemittel im Sinne der vorliegenden Erfindung sowohl Viskositätserhöhende als auch Viskositätserniedrigende Verbindungen sein.The kneading and / or shaping is carried out according to a further embodiment with the addition of at least one binder, wherein as a binder in principle any chemical compound can be used which ensures the kneading and / or deformation desired viscosity of the kneading and / or deforming mass. Accordingly, for the purposes of the present invention, binders may be both viscosity-increasing and viscosity-reducing compounds.
Als unter anderem bevorzugte Bindemittel sind beispielsweise Aluminiumoxid oder Aluminiumoxid enthaltende Binder, wie sie beispielsweise in der WO 94/29408 beschrieben sind, Siliciumdioxid, wie es beispielsweise in der EP 0 592 050 A1 beschrieben ist, Mischungen ais Siliciumdioxid und Aluminiumoxid, wie sie beispielsweise in der WO 94/13584 beschrieben sind, Tonminerale, wie sie bei- spielsweise in der JP 03-037156 A beschrieben sind, beispielsweise Montmorillonit, Kaolin, Bentonit, Halloysit, Dickit, Nacrit und Anauxit, Alkoxysilane, wie sie beispielsweise in der EP 0 102 544 B1 beschrieben sind, beispielsweise Tetraalkoxysilane wie beispielsweise Tetramethoxysilan, Tetraethoxysilan, Tetrapropoxysilan, Tetrabutoxysi- lan, oder beispielsweise Trialkoxysilane wie beispielsweise Trimethoxysilan, Triethoxy- silan, Tripropoxysilan, Tributoxysilan, Alkoxytitanate, beispielsweise Tetraalkoxytitanate wie beispielsweise Tetramethoxytitanat, Tetraethoxytitanat, Tetrapropoxytitanat, Tetra- butoxytitanat, oder beispielsweise Trialkoxytitanate wie beispielsweise Trimethoxytita- nat, Triethoxytitanat, Tripropoxytitanat, Tributoxytitanat, Alkoxyzirkonate, beispielsweise Tetraalkoxyzirkonate wie beispielsweise Tetramethoxyzirkonat, Tetraethoxyzirkonat, Tetrapropoxyzirkonat, Tetrabutoxyzirkonat, oder beispielsweise Trialkoxyzirkonate wie beispielsweise Trimethoxyzirkonat, Triethoxyzirkonat, Tripropoxyzirkonat, Tributoxyzir- konat, Silikasole, amphiphile Substanzen und/oder Graphite zu nennen.Preferred binders include, for example, alumina or alumina-containing binders such as those described in WO 94/29408, silica such as described in EP 0 592 050 A1, mixtures of silica and alumina, such as those described in U.S. Pat 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, for example, trimethoxysilane, triethoxy silane, butoxy tripropoxysilane, tributoxysilane, alkoxytitanates, for example tetraalkoxy titanates such as tetramethoxy, tetraethoxy, tetrapropoxytitanate, tetra-, or, for example, trialkoxytitanates such as Trimethoxytita- nat, triethoxytitanate, tripropoxytitanate, tributoxytitanate, alkoxyzirconates, for example tetraalkoxyzirconates such as tetramethoxyzirconate, tetraethoxyzirconate, tetrapropoxyzirconate, tetrabutoxyzirconate or for example Trialkoxyzirkonate such as trimethoxyzirconate, triethoxyzirconate, Tripropoxyzirkonat, tributoxyzirconate, silica sols, amphiphilic substance and / or Graphite.
Als viskositätssteigernde Verbindung kann beispielsweise auch, gegebenenfalls zu- sätzlich zu den oben genannten Verbindungen, eine organische Verbindung und/oder ein hydrophiles Polymer wie beispielsweise Cellulose oder ein CeIIu- losederivat wie beispielsweise Methylcellulose und/oder ein Polyacrylat und/oder einAs a viscosity-increasing compound, for example, optionally in addition to the above-mentioned compounds, an organic compound and / or a hydrophilic polymer such as cellulose or a CeIIU losederivat such as methyl cellulose and / or a polyacrylate and / or a
Polymethacrylat und/oder ein Polyvinylalkohol und/oder ein Polyvinylpyrrolidon und/oder ein Polyisobuten und/oder ein Polytetrahydrofuran und/oder ein Polyethylen- oxid eingesetzt werden.Polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran and / or a polyethylene oxide are used.
Als Anteigungsmittel kann unter anderem bevorzugt Wasser oder mindestens ein Alkohol wie beispielsweise ein Monoalkohol mit 1 bis 4 C-Atomen wie beispielsweise Methanol, Ethanol, n-Propanol, iso-Propanol, 1-Butanol, 2-Butanol, 2-Methyl-1-pro- panol oder 2-Methyl-2-propanol oder ein Gemisch aus Wasser und mindestens einem der genannten Alkohole oder ein mehrwertiger Alkohol wie beispielsweise ein Glykol, bevorzugt ein wassermischbarer mehrwertiger Alkohol, allein oder als Gemisch mit Wasser und/oder mindestens einem der genannten einwertigen Alkohole eingesetzt werden.As 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.
Weitere Additive, die zum Kneten und/oder Verformen eingesetzt werden können, sind unter anderem Amine oder Aminderivate wie beispielsweise Tetraalkylammonium- Verbindungen oder Aminoalkohole und Carbonat enthaltende Verbindungen wie etwa Calciumcarbonat. Solche weiteren Additive sind etwa in der EP 0 389 041 A1 , der EP 0 200 260 A1 oder der WO 95/19222 beschrieben.Other additives that can be used for kneading and / or shaping include amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols, and carbonate containing compounds such as calcium carbonate. Such further additives are described for example in EP 0 389 041 A1, EP 0 200 260 A1 or WO 95/19222.
Die Reihenfolge der Additive wie Templatverbindung, Binder, Anteigungsmittel, viskositätssteigernde Substanz beim Verformen und Kneten ist grundsätzlich nicht kritisch. Gemäß einer weiteren bevorzugten Ausführungsform wird der gemäß Kneten und/oder Verformen erhaltene Formkörper mindestens einer Trocknung unterzogen, die im Allgemeinen bei einer Temperatur im Bereich von 25 bis 500 °C, bevorzugt im Bereich von 50 bis 500 °C und besonders bevorzugt im Bereich von 100 bis 350 °C durchgeführt wird. Ebenso ist es möglich, im Vakuum oder unter Schutzgasatmosphäre oder durch Sprühtrocknung zu trocknen.The order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical. According to a further preferred embodiment, the molding obtained according to kneading and / or molding is subjected to at least one drying, generally at a temperature in the range of 25 to 500 ° C, preferably in the range of 50 to 500 ° C and more preferably in the range of 100 to 350 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
Gemäß einer besonders bevorzugten Ausführungsform wird im Rahmen dieses Trocknungsvorgangs mindestens eine der als Additive zugesetzten Verbindungen zumindest teilweise aus dem Formkörper entfernt.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.
Das erfindungsgemäße metallorganische Gerüstmaterial enthält Poren, insbesondere Mikro- und/oder Mesoporen. Mikroporen sind definiert als solche mit einem Durchmesser von 2 nm oder kleiner und Mesoporen sind definiert durch einen Durchmesser im Bereich von 2 bis 50 nm (Pure & Appl. Chem. 57 (1985) 603-619). Die Anwesenheit von Mikro- und/oder Mesoporen kann mit Hilfe von Sorptionsmessungen überprüft werden, wobei diese Messungen die Aufnahmekapazität der metallorganischen Gerüstmaterialien für Stickstoff bei 77 Kelvin (nach Langmuir) gemäß DIN 66131 und/oder DIN 66134 bestimmt.The organometallic framework according to the invention contains 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 (Pure & Appl. Chem. 57 (1985) 603-619). The presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the uptake capacity of the organometallic frameworks for nitrogen at 77 Kelvin (according to Langmuir) according to DIN 66131 and / or DIN 66134.
Bevorzugt liegen die Poren in Form eindimensionaler Kanäle mit einem Durchmesser von 5 bis 15 Angström, besonders bevorzugt von 7 bis 12 Ä vor.Preferably, the pores are in the form of one-dimensional channels having a diameter of 5 to 15 angstroms, more preferably 7 to 12 Å.
Vorzugsweise beträgt die spezifische Oberfläche - berechnet nach dem Langmuir- Modell (DIN 66131 , 66134) für das erfindungsgemäße metallorganische Gerüstmaterial in Pulverform mindestens 1000 m2/g, mehr bevorzugt mindestens 1200 m2/g, mehr bevorzugt mindestens 1400 m2/g, weiter mehr bevorzugt mindestens 1600 m2/g, weiter mehr bevorzugt mindestens 1800 m2/g und besonders bevorzugt mindestens 1950 m2/g.Preferably, the specific surface area - calculated according to the Langmuir model (DIN 66131, 66134) for the organometallic framework according to the invention in powder form is at least 1000 m 2 / g, more preferably at least 1200 m 2 / g, more preferably at least 1400 m 2 / g, more preferably at least 1600 m 2 / g, more preferably at least 1800 m 2 / g and particularly preferably at least 1950 m 2 / g.
Formkörper aus dem erfindungsgemäßen metallorganischen Gerüstmaterial können eine niedrigere spezifische Oberfläche besitzen; vorzugsweise jedoch mindestens 500 m2/g, mehr bevorzugt mindestens 600 m2/g, weiter mehr bevorzugt mindestens 700 m2/g, insbesondere mindestens 800 m2/g.Shaped bodies of the organometallic framework according to the invention may have a lower specific surface; but preferably at least 500 m 2 / g, more preferably at least 600 m 2 / g, even more preferably at least 700 m 2 / g, in particular at least 800 m 2 / g.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines erfindungsgemäßen porösen metallorganischen Gerüstmaterials, den Schritt enthaltend - Umsetzung eines Reaktionsgemisches enthaltend mindestens eine Aluminiumverbindung und Fumarsäure oder ein Salz davon in Gegenwart eines organischen Lösemittels bei einer vorgegebenen Temperatur und einem vorgegebenen Druck.Another object of the present invention is a method for producing a porous organometallic framework according to the invention, comprising the step Reaction of a reaction mixture comprising at least one aluminum compound and fumaric acid or a salt thereof in the presence of an organic solvent at a predetermined temperature and a predetermined pressure.
Als organische Komponente des erfindungsgemäßen porösen metallorganischen Gerüstmaterials dient Fumarsäure, die mit einer Aluminiumverbindung umgesetzt werden kann. Ebenso ist es möglich, Derivate der Fumarsäure einzusetzen. So ist es zum Beispiel denkbar, dass Fumarsäure in Form ihres Salzes eingesetzt wird. Das Salz, bei dem Fumarsäure als vollständig oder teilweise deprotoniertes Anion vorliegt, kann ein beliebig geeignetes Kation aufweisen.As the organic component of the porous organometallic framework of the invention is fumaric acid, which can be reacted with an aluminum compound. It is also possible to use derivatives of fumaric acid. For example, it is conceivable that fumaric acid is used in the form of its salt. The salt in which fumaric acid is present as a fully or partially deprotonated anion may have any suitable cation.
Solche Kationen können beispielsweise ein- oder zweiwertige, vorzugsweise einwertige Metallionen sein. Beispiele hierfür sind insbesondere Natrium- und Kaliumsalze. Ebenso sind Kationen von Ammoniumverbindungen einsetzbar. Hierbei sind insbeson- dere Ammonium selbst sowie Alkylammoniumkationen zu nennen.Such cations may be, for example, mono- or divalent, preferably monovalent metal ions. Examples of these are in particular sodium and potassium salts. Likewise, cations of ammonium compounds can be used. In particular, ammonium itself and alkylammonium cations should be mentioned here.
Die Aluminiumverbindung kann durch anodische Oxidation von metallischem Aluminium erzeugt werden. In einem solchen Fall wird das erfindungsgemäße poröse metallorganische Gerüstmaterial auf zumindest teilweise elektrochemischem Wege herge- stellt. Verfahren zur elektrochemischen Herstellung von porösen metallorganischen Gerüstmaterialien sind in WO-A 2005/049892 beschrieben. Auch die Erzeugung der Aluminiumverbindung für das erfindungsgemäße poröse metallorganische Gerüstmaterial kann auf diesem Wege hergestellt werden.The aluminum compound can be produced by anodic oxidation of metallic aluminum. In such a case, the porous organometallic framework according to the invention is prepared at least partially by electrochemical means. Methods for the electrochemical preparation of porous organometallic frameworks are described in WO-A 2005/049892. The production of the aluminum compound for the porous organometallic framework according to the invention can also be prepared in this way.
Bei der elektrochemischen Herstellung des erfindungsgemäßen porösen metallorganischen Gerüstmaterials ist bevorzugt, dass die kathodische Wiederabscheidung des Aluminiumions durch mindestens eine der folgenden Maßnahmen zumindest teilweise verhindert wird:In the electrochemical preparation of the porous organometallic framework according to the invention it is preferred that the cathodic redeposition of the aluminum ion is at least partially prevented by at least one of the following measures:
(i) Verwendung eines Elektrolyten, der die kathodische Bildung von Wasserstoff begünstigt;(i) use of an electrolyte which promotes the cathodic formation of hydrogen;
(ii) Zusatz mindestens einer Verbindung, die zu einer kathodischen Depolarisation führt;(ii) adding at least one compound resulting in cathodic depolarization;
(iii) Einsatz einer Kathode mit einer geeigneten Wasserstoffüberspannung.(iii) use of a cathode with a suitable hydrogen overvoltage.
Das Verfahren kann in einer ungeteilten Elektrolysezelle durchgeführt werden. Speziell geeignete Zellen sind Spaltzellen oder Plattenstapelzellen. Diese können bipolar ge- schaltet sein. Als Reaktionsmedium eignet sich beispielsweise Methanol, Ethanol, Di- methylformamid, Diethylformamid oder ein Gemisch aus zwei oder mehr dieser Lösemittel.The process can be carried out in an undivided electrolysis cell. Especially suitable cells are split cells or plate-stack cells. These can be switched bipolar. As a reaction medium, for example, methanol, ethanol, di- methylformamide, diethylformamide or a mixture of two or more of these solvents.
In dem Reaktionsgemisch kann/können weiterhin ein Leitsalz oder mehrere Leitsalze vorhanden sein. Hierbei kann das Leitsalz als Kationkomponente ein quartäres Ammonium und als Anionkomponente ein Alkoxysulfat aufweisen. Der Gesamtfeststoffgehalt sollte im Bereich von größer oder gleich 0,5 Gew.-% liegen.In the reaction mixture, a conductive salt or a plurality of conductive salts may furthermore be present. In this case, the conductive salt can have a quaternary ammonium as the cation component and an alkoxy sulfate as the anion component. The total solids content should be in the range of greater than or equal to 0.5% by weight.
Die Umsetzung in dem erfindungsgemäßen Verfahren zur Herstellung des erfindungs- gemäßen metallorganischen Gerüstmaterials kann auch auf klassischem Wege erfolgen. Hierbei ist die Aluminiumverbindung typischerweise ein Aluminiumsalz.The reaction in the process according to the invention for the preparation of the organometallic framework according to the invention can also be carried out by conventional means. Here, the aluminum compound is typically an aluminum salt.
Das Aluminiumsalz kann in Form eines Alkoholats, Acetonats, Halegonids, Sulfits, als Salz einer organischen oder anorganischen, Sauerstoff enthaltenden Säure oder einer Mischung davon vorliegen.The aluminum salt may be in the form of an alcoholate, acetonate, halegonide, sulfite, salt of an organic or inorganic oxygen-containing acid, or a mixture thereof.
Ein Alkoholat ist beispielsweise ein Methanolat, Ethanolat, n-Propanolat, i-Propanolat, n-Butanolat, i-Butanolat, t-Butanolat oder Phenolat.An alcoholate is, for example, a methoxide, ethanolate, n-propoxide, i-propanolate, n-butoxide, i-butoxide, t-butoxide or phenolate.
Ein Acetonat ist beispielsweise Acetylacetonat.An acetonate is, for example, acetylacetonate.
Ein Halogenid ist beispielsweise Chlorid, Bromid oder lodid.A halide is, for example, chloride, bromide or iodide.
Eine organische, Sauerstoff enthaltende Säure ist beispielsweise Ameisensäure, Es- sigsäure, Propionsäure oder andere Alkylmonocarbonsäuren.An organic, oxygen-containing acid is, for example, formic acid, acetic acid, propionic acid or other alkyl monocarboxylic acids.
Eine anorganische, Sauerstoff enthaltende Säure ist beispielsweise Schwefelsäure, schweflige Säure, Phosphorsäure oder Salpetersäure.An inorganic, oxygen-containing acid is, for example, sulfuric acid, sulfurous acid, phosphoric acid or nitric acid.
Weiter bevorzugte Aluminiumverbindungen sind anorganische Aluminiumsalze wie Aluminiumchlorid, Aluminiumbromid, Aluminiumhydrogensulfat, Aluminiumdihydro- genphosphat, Aluminiummonohydrogenphosphat, Aluminiumphosphat, Aluminiumnitrat.Further preferred aluminum compounds are inorganic aluminum salts such as aluminum chloride, aluminum bromide, aluminum hydrogen sulfate, aluminum dihydrogen phosphate, aluminum monohydrogen phosphate, aluminum phosphate, aluminum nitrate.
Die Aluminiumverbindung kann gegebenenfalls Hydratwasser aufweisen, was bevorzugt ist. Besonders bevorzugt sind als Aluminiumverbindung die Hydrate des Chlorids, Nitrats sowie Sulfats.The aluminum compound may optionally have water of hydration, which is preferable. The hydrates of the chloride, nitrate and sulfate are particularly preferred as the aluminum compound.
Die Umsetzung in dem erfindungsgemäßen Verfahren zur Herstellung des erfindungs- gemäßen porösen metallorganischen Gerüstmaterials erfolgt zumindest in Gegenwart eines organischen Lösemittels. Hierbei können Solvothermalbedingungen eingesetzt werden.The reaction in the process according to the invention for the preparation of the porous organometallic framework according to the invention takes place at least in the presence an organic solvent. Solvothermal conditions can be used here.
Unter dem Begriff "thermal" ist im Rahmen der vorliegenden Erfindung ein Herstellver- fahren zu verstehen, bei dem die Umsetzung zum erfindungsgemäßen porösen metallorganischen Gerüstmaterial in einem Druckbehälter derart durchgeführt wird, dass dieser während der Umsetzung verschlossen ist und erhöhte Temperatur angelegt wird, so dass aufgrund des Dampfdruckes von vorhandenem Lösemittel sich ein Druck innerhalb des Reaktionsmediums im Druckbehälter aufbaut.In the context of the present invention, the term "thermal" is to be understood as meaning a preparation process in which the conversion to the porous organometallic framework according to the invention is carried out in a pressure vessel such that it is closed during the reaction and elevated temperature is applied, so that due to the vapor pressure of existing solvent, a pressure builds up within the reaction medium in the pressure vessel.
Vorzugsweise erfolgt die Umsetzung nicht in Wasser enthaltendem Medium und ebenso nicht unter Solvothermalbedingungen.Preferably, the reaction does not occur in water-containing medium and also not under solvothermal conditions.
Die Umsetzung in dem erfindungsgemäßen Verfahren erfolgt demzufolge vorzugswei- se in Gegenwart eines nicht-wässrigen Lösemittels.The reaction in the process according to the invention is therefore preferably carried out in the presence of a non-aqueous solvent.
Die Umsetzung erfolgt vorzugsweise bei einem Druck von 1 bar bis 16 bar (absolut), vorzugsweise 1 bis 3 bar (absolut). Weiter bevorzugt beträgt der Druck jedoch höchstens 1230 mbar (absolut). Insbesondere bevorzugt findet die Umsetzung bei Atmo- sphärendruck statt. Hierbei kann es jedoch apparativ bedingt zu leichten Über- oder Unterdrücken kommen. Daher ist im Rahmen der vorliegenden Erfindung unter dem Begriff "Atmosphärendruck" derjenige Druckbereich zu verstehen, der sich aus dem tatsächlichen vorliegenden Atmosphärendruck ± 150 mbar ergibt.The reaction is preferably carried out at a pressure of 1 bar to 16 bar (absolute), preferably 1 to 3 bar (absolute). More preferably, however, the pressure is at most 1230 mbar (absolute). Particularly preferably, the reaction takes place at atmospheric pressure. However, this may lead to slight overpressure or depression due to the apparatus. Therefore, in the context of the present invention, the term "atmospheric pressure" is to be understood as the pressure range which results from the actual atmospheric pressure of ± 150 mbar.
Die Umsetzung findet vorzugsweise in einem Temperaturbereich von 100°C bis 200°C statt. Vorzugsweise liegt die Temperatur im Bereich von 1 10°C bis 170°C. Weiterhin bevorzugt liegt die Temperatur in einem Bereich von 120°C bis 150°C.The reaction preferably takes place in a temperature range from 100.degree. C. to 200.degree. Preferably, the temperature is in the range of 1 10 ° C to 170 ° C. Further preferably, the temperature is in a range of 120 ° C to 150 ° C.
Das Reaktionsgemisch kann weiterhin eine Base aufweisen. Dies dient insbesondere dazu, dass bei Einsatz der Carbonsäure als mindestens zweizähniger organischer Verbindung diese leicht löslich ist. Durch die Verwendung eines organischen Lösemittels ist es häufig nicht erforderlich, eine solche Base einzusetzen. Nichts desto trotz kann das Lösemittel für das erfindungsgemäße Verfahren derart gewählt werden, dass dieses als solches basisch reagiert, was jedoch nicht zwingend für die Durchführung des erfindungsgemäßen Verfahrens sein muss.The reaction mixture may further comprise a base. This serves, in particular, that when the carboxylic acid is used as the at least bidentate organic compound, it is readily soluble. By using an organic solvent, it is often not necessary to use such a base. Nevertheless, the solvent for the process according to the invention can be chosen such that it reacts basicly as such, but this does not necessarily have to be for carrying out the process according to the invention.
Ebenso kann eine Base eingesetzt werden. Bevorzugt ist jedoch, dass keine zusätzliche Base eingesetzt wird. Es ist weiterhin vorteilhaft, dass die Umsetzung unter Rühren stattfinden kann, was auch bei einem Scale-up vorteilhaft ist.Likewise, a base can be used. However, it is preferred that no additional base is used. It is also advantageous that the reaction can take place with stirring, which is also advantageous in a scale-up.
Das (nicht-wässrige) organische Lösemittel ist vorzugsweise ein d-6-Alkanol, Di- methylsulfoxid (DMSO), N,N-Dimethylformamid (DMF), N,N-Diethylformamid (DEF), N,N-Dimethylacetamid (DMAc), Acetonitril, Toluol, Dioxan, Benzol, Chlorbenzol, Me- thylethylketon (MEK), Pyridin, Tetra hydrofu ran (THF), Essigsäureethylester, gegebenenfalls halogeniertes d^oo-Alkan, Sulfolan, Glykol, N-Methylpyrrolidon (NMP), gam- ma-Butyrolacton, alicyclische Alkohole wie Cyclohexanol, Ketone, wie Aceton oder Acetylaceton, Cycloketone, wie Cyclohexanon, Sulfolen oder Mischungen davon.The (non-aqueous) organic solvent is preferably a d-6-alkanol, dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc) , Acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, optionally halogenated d, ooalkane, sulfolane, glycol, N-methylpyrrolidone (NMP), glycerol. ma-butyrolactone, alicyclic alcohols such as cyclohexanol, ketones such as acetone or acetylacetone, cycloketones such as cyclohexanone, sulfolene or mixtures thereof.
Ein C-ι-6-Alkanol bezeichnet einen Alkohol mit 1 bis 6 C-Atomen. Beispiele hierfür sind Methanol, Ethanol, n-Propanol, i-Propanol, n-Butanol, i-Butanol, t-Butanol, Pentanol, Hexanol sowie Gemische davon.A C-ι- 6- alkanol denotes an alcohol having 1 to 6 C atoms. Examples of these are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol and mixtures thereof.
Ein gegebenenfalls halogeniertes bezeichnet ein Alkan mit 1 bis 200 C-Atomen, wobei ein oder mehrere bis hin zu allen Wasserstoffatomen durch Halogen, vorzugsweise Chlor oder Fluor, insbesondere Chlor, ersetzt sein kann bzw. können. Beispiele hierfür sind Chloroform, Dichlormethan, Tetrachlormethan, Dichlorethan, He- xan, Heptan, Oktan sowie Gemische davon.An optionally halogenated denotes an alkane having 1 to 200 carbon atoms, where one or more up to all hydrogen atoms may be replaced by halogen, preferably chlorine or fluorine, in particular chlorine, or may be. Examples thereof are chloroform, dichloromethane, tetrachloromethane, dichloroethane, hexane, heptane, octane and mixtures thereof.
Bevorzugte Lösemittel sind DMF, DEF, DMAc und NMP. Besonders bevorzugt ist DMF.Preferred solvents are DMF, DEF, DMAc and NMP. Particularly preferred is DMF.
Der Begriff "nicht-wässrig" bezieht sich vorzugsweise auf ein Lösemittel, das einen Höchstwassergehalt von 10 Gew.-%, mehr bevorzugt 5 Gew.-%, weiterhin mehr bevorzugt 1 Gew.-%, weiterhin bevorzugt 0,1 Gew.-%, besonders bevorzugt 0,01 Gew.-% bezogen auf das Gesamtgewicht des Lösemittels nicht überschreitet.The term "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, further preferably 0.1% by weight. , particularly preferably 0.01 wt .-% based on the total weight of the solvent does not exceed.
Vorzugsweise beträgt der Höchstwassergehalt während der Umsetzung 10 Gew.-%, mehr bevorzugt 5 Gew.-% und weiterhin mehr bevorzugt 1 Gew.-%.Preferably, the maximum water content during the reaction is 10% by weight, more preferably 5% by weight, and still more preferably 1% by weight.
Der Begriff "Lösemittel" betrifft reine Lösemittel sowie Gemische von unterschiedlichen Lösemitteln.The term "solvent" refers to pure solvents as well as mixtures of different solvents.
Weiterhin bevorzugt schließt sich an den Verfahrensschritt der Umsetzung der mindestens einen Metallverbindung mit der mindestens einen mindestens zweizähnigen organischen Verbindung ein Calcinierungsschritt an. Die hierbei eingestellte Temperatur beträgt typischerweise mehr als 250°C, bevorzugt 300 bis 400°C. Aufgrund des Calcinierungsschrittes kann die in den Poren befindliche mindestens zweizähnige organische Verbindung entfernt werden.Further preferably, the process 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. Due to the calcination step, the at least bidentate organic compound present in the pores can be removed.
Ergänzend oder alternativ hierzu kann die Entfernung der mindestens zweizähnigen organischen Verbindung (Ligand) aus den Poren des porösen metallorganischen Gerüstmaterials durch die Behandlung des gebildeten Gerüstmaterials mit einem nicht- wässrigen Lösemittel erfolgen. Hierbei wird in einer Art "Extraktionsverfahren" der Ligand entfernt und gegebenenfalls im Gerüstmaterial durch ein Lösemittelmolekül ersetzt.Additionally or alternatively, 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. In this case, the ligand is removed in a kind of "extraction process" and optionally replaced in the framework by a solvent molecule.
Die Behandlung erfolgt vorzugsweise mindestens 30 Minuten und kann typischerweise bis zu 7 Tagen durchgeführt werden. Dies kann bei Raumtemperatur oder erhöhter Temperatur geschehen. Vorzugsweise erfolgt dies unter erhöhter Temperatur, beispielsweise bei mindestens 40°C, bevorzugt 60°C. Weiterhin bevorzugt erfolgt die Ex- traktion bei der Siedetemperatur des eingesetzten Lösemittels statt (unter Rückfluss).The treatment is preferably at least 30 minutes and may typically be carried out for up to 7 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 of (under reflux).
Die Behandlung kann in einem einfachen Kessel durch Aufschlämmen und Rühren des Gerüstmaterials erfolgen. Es können auch Extraktionsapparaturen wie Soxhlet- Apparaturen, insbesondere technische Extraktionsapparaturen, eingesetzt werden.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.
Als geeignete Lösemittel können die oben genannten verwendet werden, also beispielsweise d-6-Alkanol, Dimethylsulfoxid (DMSO), N,N-Dimethylformamid (DMF), N,N-Diethylformamid (DEF), N,N-Dimethylacetamid (DMAc), Acetonitril, Toluol, Dioxan, Benzol, Chlorbenzol, Methylethylketon (MEK), Pyridin, Tetrahydrofuran (THF), Essig- säureethylester, gegebenenfalls halogeniertes Ci-2oo-Alkan, Sulfolan, Glykol, N- Methylpyrrolidon (NMP), gamma-Butyrolacton, alicyclische Alkohole wie Cyclohexanol, Ketone, wie Aceton oder Acetylaceton, Cycloketone, wie Cyclohexanon oder Mischungen davon.As suitable solvents, the above-mentioned can be used, that is, for example, d-6-alkanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), acetic acid ethyl ester, 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 or mixtures thereof.
Bevorzugt sind Methanol, Ethanol, Propanol, Aceton, MEK und Mischungen davon.Preferred are methanol, ethanol, propanol, acetone, MEK and mixtures thereof.
Ein ganz besonders bevorzugtes Extraktionslösemittel ist Methanol.A most preferred extraction solvent is methanol.
Das verwendete Lösemittel zur Extraktion kann gleich oder verschieden zu demjenigen für die Umsetzung der mindestens einen Metallverbindung mit der mindestens einen mindestens zweizähnigen organischen Verbindung sein. Es ist bei der "Extraktion" nicht unbedingt erforderlich aber bevorzugt, dass das Lösemittel wasserfrei ist. Es ist bevorzugt, dass in dem erfindungsgemäßen Verfahren das molare Verhältnis Aluminiumverbindung zu Fumarsäure oder einem ihrer Salze im Bereich von 0,3 : 1 bis 1 ,7 : 1 liegt. Mehr bevorzugt liegt das Verhältnis im Bereich von 0,7 : 1 bis 1 ,2 : 1.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. It is not essential in the "extraction" but preferred that the solvent is anhydrous. It is preferred that in the process according to the invention the molar ratio of aluminum compound to fumaric acid or one of its salts is in the range of 0.3: 1 to 1.7: 1. More preferably, the ratio is in the range of 0.7: 1 to 1.2: 1.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen porösen metallorganischen Gerüstmaterials zur Aufnahme mindestens eines Stoffes, zu dessen Speicherung, Abtrennung, kontrollierten Abgabe, chemischen Umsetzung oder als Träger.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, chemical reaction or as a carrier.
Vorzugsweise handelt es sich bei dem mindestens einen Stoff um ein Gas oder Gasgemisch. Auch Flüssigkeiten sind möglich.Preferably, the at least one substance is a gas or gas mixture. Also liquids are possible.
Verfahren zur Speicherung mit Hilfe von metallorganischen Gerüstmaterialien im Allgemeinen sind in WO-A 2005/003622, WO-A 2003/064030, WO-A 2005/049484, WO- A 2006/089908 sowie DE-A 10 2005 012 087 beschrieben. Die dort beschriebenen Verfahren können auch für das erfindungsgemäße metallorganische Gerüstmaterial eingesetzt werden. Bevorzugte Gase zur Speicherung sind Methan oder Wasserstoff.Methods for storage with the aid of organometallic frameworks in general are described in WO-A 2005/003622, WO-A 2003/064030, WO-A 2005/049484, WO-A 2006/089908 and DE-A 10 2005 012 087. The processes described there can also be used for the organometallic framework according to the invention. Preferred gases for storage are methane or hydrogen.
Verfahren zur Trennung beziehungsweise Reinigung mit Hilfe von metallorganischen Gerüstmaterialien im Allgemeinen sind in der EP-A 1 674 555, DE-A 10 2005 000938 und in der deutschen Patentanmeldung mit der Anmeldenummer DE-A 10 2005 022 844 beschrieben. Die dort beschriebenen Verfahren können auch für das erfindungsgemäße metallorganische Gerüstmaterial eingesetzt werden. Ein bevorzugt abzutrennendes Gas ist Kohlendioxid, insbesondere aus einem weiterhin Kohlenmonoxid ent- haltenden Gasgemisch.Methods for the separation or purification with the aid of organometallic framework materials in general are described in EP-A 1 674 555, DE-A 10 2005 000938 and in the German patent application with the application number DE-A 10 2005 022 844. The processes described there can also be used for the organometallic framework according to the invention. A preferred gas to be separated off is carbon dioxide, in particular from a gas mixture which furthermore contains carbon monoxide.
Sofern das erfindungsgemäße poröse metallorganische Gerüstmaterial zur Speicherung eingesetzt wird, erfolgt dies vorzugsweise in einem Temperaturbereich von - 200°C bis +80°C. Mehr bevorzugt ist ein Temperaturbereich von -40°C bis +80°C. Ein bevorzugter Druckbereich liegt bei 20 bar bis 1000 bar (absolut), insbesondere 100 bar bis 400 bar.If the 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. A preferred pressure range is 20 bar to 1000 bar (absolute), in particular 100 bar to 400 bar.
Im Rahmen der vorliegenden Erfindung werden vereinfachend die Begriffe „Gas" und „Flüssigkeit" verwendet, wobei hier jedoch ebenso Gasgemische sowie Flüssigkeits- gemische beziehungsweise flüssige Lösungen unter dem Begriff „Gas" beziehungsweise „Flüssigkeit" zu verstehen sind.For the purposes of the present invention, the terms "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".
Bevorzugte Gase sind Wasserstoff, Erdgas, Stadtgas, Kohlenwasserstoffe, insbesondere Methan, Ethan, Ethen, Acetylen, Propan, n-Butan sowie i-Butan, Kohlenmonoxid, Kohlendioxid, Stickoxide, Sauerstoff, Schwefeloxide, Halogene, halogenide Kohlen- Wasserstoffe, NF3, SF6, Ammoniak, Borane, Phosphane, Schwefelwasserstoff, Amine, Formaldehyd, Edelgase, insbesondere Helium, Neon, Argon, Krypton sowie Xenon.Preferred gases are hydrogen, natural gas, town gas, hydrocarbons, in particular methane, ethane, ethene, acetylene, propane, n-butane and also i-butane, carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, sulfur oxides, halogens, halogenated carbon atoms. Hydrogen, NF 3 , SF 6 , ammonia, boranes, phosphines, hydrogen sulfide, amines, formaldehyde, noble gases, especially helium, neon, argon, krypton and xenon.
Besonders bevorzugt handelt es sich bei dem Gas um Kohlendioxid, das aus einem Kohlendioxid enthaltenden Gasgemisch abgetrennt wird. Bevorzugt weist dabei das Gasgemisch neben Kohlendioxid wenigstens H2, CH4 oder Kohlenmonoxid auf. Insbesondere weist dabei das Gasgemisch neben Kohlendioxid Kohlenmonoxid auf. Ganz besonders bevorzugt sind Gemische, die wenigstens 10 und höchsten 45 Vol.-% Kohlendioxid und wenigstens 30 und höchstens 90 Vol.-% Kohlenmonoxid enthalten.Particularly preferably, the gas is carbon dioxide which is separated from a gas mixture containing carbon dioxide. Preferably, the gas mixture in addition to carbon dioxide at least H 2 , CH 4 or carbon monoxide. In particular, the gas mixture has carbon monoxide in addition to carbon dioxide. Very particular preference is given to mixtures which contain at least 10 and at most 45% by volume of carbon dioxide and at least 30 and at most 90% by volume of carbon monoxide.
Eine bevorzugte Ausführungsform ist die Druckwechseladsorption mit mehreren parallelen Adsorberreaktoren, wobei die Adsorbensschüttung ganz oder teilweise aus dem erfindungsgemäßen Material besteht. Die Adsorptionsphase findet für die CO2/CO- Trennung bevorzugt bei einem CO2-Partialdruck von 0,6 bis 3 bar und Temperatur von wenigstens 20, jedoch höchstens 70°C statt. Zur Desorption des adsorbierten Kohlendioxids wird der Gesamtdruck in dem betreffenden Adsorberreaktor üblicherweise abgesenkt auf werte zwischen 100 mbar und 1 bar.A preferred embodiment is the pressure swing adsorption with a plurality of parallel adsorber reactors, wherein the adsorbent bulk consists wholly or partly of the material according to the invention. The adsorption phase takes place for the CO 2 / CO separation preferably at a CO 2 partial pressure of 0.6 to 3 bar and a temperature of at least 20 but not more than 70 ° C. For desorption of the adsorbed carbon dioxide, the total pressure in the relevant adsorber reactor is usually lowered to values between 100 mbar and 1 bar.
Weiterhin bevorzugt ist die Verwendung des erfindungsgemäßen Gerüstmaterials zum Speichern eines Gases bei einem Mindestdruck von 100 bar (absolut). Mehr bevorzugt beträgt der Mindestdruck 200 bar (absolut), insbesondere 300 bar (absolut). Hierbei handelt es sich besonders bevorzugt bei dem Gas um Wasserstoff oder Methan.Further preferred is the use of the framework material according to the invention for storing a gas at a minimum pressure of 100 bar (absolute). More preferably, the minimum pressure is 200 bar (absolute), in particular 300 bar (absolute). These are particularly preferably in the gas to hydrogen or methane.
Bei dem mindestens einen Stoff kann es sich jedoch auch um eine Flüssigkeit handeln. Beispiele für eine solche Flüssigkeit sind Desinfektionsmittel, anorganische oder organische Lösemittel, Treibstoffe - insbesondere Benzin oder Diesel -, Hydraulik-, Kühler-, Bremsflüssigkeit oder ein Öl, insbesondere Maschinenöl. Weiterhin kann es sich bei der Flüssigkeit um halogenierte aliphatische oder aromatische, cyclische oder acyc- lische Kohlenwasserstoffe oder Mischungen davon handeln. Insbesondere kann die Flüssigkeit Aceton, Acetonitril, Anilin, Anisol, Benzol, Benzonitril, Brombenzol, Butanol, tert.-Butanol, Chinolin, Chlorbenzol, Chloroform, Cyclohexan, Diethylenglykol, Diethyl- ether, Dimethylacetamid, Dimethylformamid, Dimethylsulfoxid, Dioxan, Eisessig, Essigsäureanhydrid, Essigsäureethylester, Ethanol, Ethylencarbonat, Ethylendichlorid, Ethy- lenglykol, Ethylenglykoldimethylether, Formamid, Hexan, Isopropanol, Methanol, Me- thoxypropanol, 3-Methyl-1 -butanol, Methylenchlorid, Methylethylketon, N-Methyl- formamid, N-Methylpyrrolidon, Nitrobenzol, Nitromethan, Piperidin, Propanol, Propy- lencarbonat, Pyrridin, Schwefelkohlenstoff, Sulfolan, Tetrachlorethen, Tetrachlorkohlenstoff, Tetrahydrofuran, Toluol, 1 ,1 ,1-Trichlorethan, Trichlorethylen, Triethylamin, Triethylenglykol, Triglyme, Wasser oder Mischungen hiervon handeln. Weiterhin kann der mindestens eine Stoff ein Geruchsstoff sein.However, the at least one substance may also be 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. Furthermore, the liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof. In particular, the liquid acetone, acetonitrile, aniline, anisole, benzene, benzonitrile, bromobenzene, butanol, tert-butanol, quinoline, chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dioxane, glacial acetic acid, acetic anhydride , Ethyl acetate, ethanol, ethylene carbonate, ethylene dichloride, ethylene glycol, ethylene glycol dimethyl ether, formamide, hexane, isopropanol, methanol, methoxypropanol, 3-methyl-1-butanol, methylene chloride, methyl ethyl ketone, N-methylformamide, N-methylpyrrolidone, nitrobenzene , Nitromethane, piperidine, propanol, propylene carbonate, pyrridine, carbon disulfide, sulfolane, tetrachloroethene, carbon tetrachloride, tetrahydrofuran, toluene, 1,1,1-trichloroethane, trichlorethylene, triethylamine, triethylene glycol, triglyme, water or mixtures thereof. Furthermore, the at least one substance may be an odorant.
Vorzugsweise handelt es sich bei dem Geruchsstoff um eine flüchtige organische oder anorganische Verbindung, die mindestens eines der Elemente Stickstoff, Phosphor, Sauerstoff, Schwefel, Fluor, Chlor, Brom oder lod enthält oder ein ungesättigter oder aromatischer Kohlenwasserstoff oder ein gesättigter oder ungesättigter Aldehyd oder ein Keton ist. Mehr bevorzugte Elemente sind Stickstoff, Sauerstoff, Phosphor, Schwefel, Chlor, Brom; insbesondere bevorzugt sind Stickstoff, Sauerstoff, Phosphor und Schwefel.Preferably, 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.
Insbesondere handelt es sich bei dem Geruchsstoff um Ammoniak, Schwefelwasserstoff, Schwefeloxide, Stickoxide, Ozon, cyclische oder acyclische Amine, Thiole, Thio- ether sowie Aldehyde, Ketone, Ester, Ether, Säuren oder Alkohole. Besonders bevorzugt sind Ammoniak, Schwefelwasserstoff, organische Säuren (bevorzugt Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovaleriansäure, Capron- säure, Heptylsäure, Laurinsäure, Pelargonsäure) sowie cyclische oder acyclische Kohlenwasserstoffe, die Stickstoff oder Schwefel enthalten sowie gesättigte oder ungesättigte Aldehyde, wie Hexanal, Heptanal, Oktanal, Nonanal, Decanal, Octenal oder No- nenal und insbesondere flüchtige Aldehyde wie Butyraldehyd, Propionaldehyd, Acetal- dehyd und Formaldehyd und weiterhin Treibstoffe wie Benzin, Diesel (Inhaltsstoffe).In particular, 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. Particular preference is given to 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) and also 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).
Bei den Geruchsstoffen kann es sich auch um Riechstoffe, die beispielsweise zur Herstellung von Parfümen verwendet werden, handeln. Beispielhaft seien als Riechstoffe oder Öle, die solche Riechstoffe freisetzen zu nennen: ätherische Öle, Basilikumöl, Geranienöl, Minzöl, Canangabaumöl, Kardamomöl, Lavendelöl, Pfefferminzöl, Muskat- Öl, Kamillenöl, Eukalyptusöl, Rosmarinöl, Zitronenöl, Limettenöl, Orangenöl, Bergamot- tenöl, Muskateller Salbeiöl, Korianderöl, Zypressenöl, 1 ,1-Dimethoxy-2-pherylethan, 2,4-Dimethyl-4-phenyltetrahydrofuran, Dimethyltetrahydrobenzaldehyd, 2,6-Dimethyl-7- octen-2-ol, 1 ,2-Diethoxy-3,7-dimethyl-2,6-octadien, Phenylacetaldehyd, Rosenoxid, Ethyl-2-methylpentanoat, 1-(2,6,6-Trimethyl-1 ,3-cyclohexadien-1-yl)-2-buten-1-on,The odorous substances may also be fragrances which are used, for example, for the production of perfumes. Examples of such 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 , Muscat 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-methyl-pentanoate, 1- (2,6,6-trimethyl-1,3-cyclohexadien-1-yl) -2-butene-1 on,
Ethylvanillin, 2,6-Dimethyl-2-octenol, 3,7-Dimethyl-2-octenol, tert-Butylcyclohexyl- acetat, Anisylacetate, Allylcyclohexyloxyacetat, Ethyllinalool, Eugenol, Cumarin, Ethyl- acetacetat, 4-Phenyl-2,4,6-trimethyl-1 ,3-dioxan, 4-Methylen-3,5,6,6-tetramethyl-2- heptanon, Ethyltetrahydrosafranat, Geranylnitril, cis-3-Hexen-1-ol, cis-3-Hexenylacetat, cis-3-Hexenylmethylcarbonate, 2,6-Dimethyl-5-hepten-1-al, 4-(Tricyclo[5.2.1.0]decyli- dene)-8-butanal, 5-(2,2,3-Trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, p-tert-Butyl- alpha-methylhydrozimtaldehyd, Ethyl[5.2.1.0]tricyclodecancarboxylat, Geraniol, Citro- nellol, Citral, Linalool, Linalylacetat, Jonone, Phenylethanol oder Mischungen hiervon. Im Rahmen der vorliegenden Erfindung weist ein flüchtiger Geruchsstoff vorzugsweise einen Siedepunkt oder Siedepunktsbereich von weniger als 300°C auf. Mehr bevorzugt ist der Geruchsstoff eine leicht flüchtige Verbindung oder Gemisch. Insbesondere bevorzugt weist der Geruchsstoff einen Siedepunkt oder Siedebereich von weniger als 250°C, mehr bevorzugt weniger als 230°C, insbesondere bevorzugt weniger als 200°C auf.Ethyl vanillin, 2,6-dimethyl-2-octenol, 3,7-dimethyl-2-octenol, tert-butyl cyclohexyl acetate, anisyl acetates, allyl cyclohexyloxyacetate, ethyllinalool, eugenol, coumarin, ethyl acetoacetate, 4-phenyl-2,4, 6-trimethyl-1,3-dioxane, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, ethyltetrahydrosafranate, geranylnitrile, cis-3-hexen-1-ol, cis-3-hexenylacetate, cis- 3-hexenylmethylcarbonates, 2,6-dimethyl-5-hepten-1-al, 4- (tricyclo [5.2.1.0] decylidenes) -8-butanal, 5- (2,2,3-trimethyl-3-cyclopentenyl ) -3-methylpentan-2-ol, p-tert-butyl-alpha-methylhydrocinnamaldehyde, ethyl [5.2.1.0] tricyclodecanecarboxylate, geraniol, citronellol, citral, linalool, linalyl acetate, ionone, phenylethanol or mixtures thereof. In the present invention, 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.
Bevorzugt sind ebenfalls Geruchsstoffe, die eine hohe Flüchtigkeit aufweisen. Als Maß für die Flüchtigkeit kann der Dampfdruck herangezogen werden. Im Rahmen der vor- liegenden Erfindung weist ein flüchtiger Geruchsstoff vorzugsweise einen Dampfdruck von mehr als 0,001 kPa (20°C) auf. Mehr bevorzugt ist der Geruchsstoff eine leicht flüchtige Verbindung oder Gemisch. Insbesondere bevorzugt weist der Geruchsstoff einen Dampfdruck von mehr als 0,01 kPa (20°C) auf, mehr bevorzugt einen Dampfdruck von mehr als 0,05 kPa (20°C) auf. Besonders bevorzugt weisen die Geruchsstof- fe einen Dampfdruck von mehr als 0,1 kPa (20°C) auf.Also preferred are odors which have a high volatility. As a measure of the volatility of the vapor pressure can be used. In the context of the present invention, a volatile odorant preferably has a vapor pressure of more 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). Particularly preferably, the odorants have a vapor pressure of more than 0.1 kPa (20 ° C.).
Beispiele, bei der eine chemische Umsetzung in Gegenwart des erfindungsgemäßen metallorganischen Gerüstmaterials stattfinden kann, stellen die Alkoxylierung von Mo- noolen sowie Polyolen dar. Die Durchführung solcher Alkoxylierungen sind WO-A 03/035717 sowie WO-A 2005/03069 beschrieben. Ebenso kann das erfindungsgemäße poröse metallorganische Gerüstmaterial zur Epoxidierung sowie Herstellung von Polyalkylencarbonaten und Wasserstoffperoxid eingesetzt werden. Solche Reaktionen sind in WO-A 03/101975, WO-A 2004/037895 sowie US-A 2004/081611 beschrieben.Examples in which a chemical reaction can take place in the presence of the organometallic framework according to the invention are the alkoxylation of monools and polyols. The performance of such alkoxylations is described in WO-A 03/035717 and WO-A 2005/03069. Likewise, the porous organometallic framework according to the invention for epoxidation and preparation of polyalkylene and hydrogen peroxide can be used. Such reactions are described in WO-A 03/101975, WO-A 2004/037895 and US-A 2004/081611.
Besonders bevorzugt sind katalytische Umsetzungen.Particularly preferred are catalytic reactions.
Darüber hinaus kann das erfindungsgemäße metallorganische Gerüstmaterial als Träger, insbesondere als Träger eines Katalysators, dienen.In addition, the organometallic framework according to the invention can serve as a carrier, in particular as a carrier of a catalyst.
BeispieleExamples
Beispiel 1 Herstellung eines reinen Al-Fumarat metallorganisches GerüstmaterialExample 1 Preparation of a pure Al fumarate organometallic framework
(MOF)(MOF)
17,91 g AICI3 *6H2O und 9,04 g Fumarsäure (LinkeπAI-Verhältnis = 1 ,05 mol/mol) wer- den in einem Glaskolben in 550 ml DMF suspendiert (Feststoffgehalt = 0,05 g/g) und 17 h unter Rückfluss (130°C) gerührt. Der entstandene Feststoff wird abfiltriert und mit 3 x 100 ml Aceton und 2 x 100 ml Methanol gewaschen. Die Filtrierzeit liegt bei kleiner 30 Sekunden. Anschließend wird die Substanz im Vakuumtrockenschrank bei 100°C 16 h getrocknet. Es werden 11 ,4g eines weißen Vorprodukts erhalten. Die N2-Oberfläche wird mit 1155 m2/g (Langmuir) bestimmt.17.91 g of AICI 3 * 6H 2 O and 9.04 g of fumaric acid (LinkeπAI ratio = 1.05 mol / mol) are suspended in a glass flask in 550 ml of DMF (solids content = 0.05 g / g) and Stirred at reflux (130 ° C) for 17 h. The resulting solid is filtered off and washed with 3 x 100 ml of acetone and 2 x 100 ml of methanol. The filtration time is less than 30 seconds. The substance is then dried in a vacuum oven at 100 ° C for 16 h. There are obtained 11, 4g of a white precursor. The N 2 surface is determined to be 1155 m 2 / g (Langmuir).
Beispiel 2 Herstellung eines reinen AI-Fumarat-MOFExample 2 Preparation of a pure Al fumarate MOF
17,91 g AICI3 *6H2O und 10,34 g Fumarsäure (LinkeπAI-Verhältnis = 1 ,2 mol/mol) werden in einem Glaskolben in 550 ml DMF suspendiert (Feststoffgehalt = 0,051 g/g) und 17 h unter Rückfluss (130°C) gerührt. Der entstandene Feststoff wird abfiltriert und mit 3 x 100 ml Aceton und 2 x 100 ml Methanol gewaschen. Anschließend wird die Sub- stanz im Vakuumtrockenschrank bei 100°C 16 h getrocknet. Es werden 1 1 ,4g eines weißen Vorprodukts erhalten. Die N2-Oberfläche wird mit 1 149 m2/g (Langmuir) bestimmt.17.91 g AICI 3 * 6H 2 O and 10.34 g fumaric acid (LinkeπAI ratio = 1, 2 mol / mol) are suspended in a glass flask in 550 ml of DMF (solids content = 0.051 g / g) and 17 h under reflux (130 ° C) stirred. The resulting solid is filtered off and washed with 3 x 100 ml of acetone and 2 x 100 ml of methanol. Subsequently, the substance is dried in a vacuum drying oven at 100 ° C. for 16 h. There are obtained 1 1, 4g of a white precursor. The N 2 surface is determined to be 1 149 m 2 / g (Langmuir).
Beispiel 3 Herstellung eines reinen AI-Fumarat-MOFs 17,91 g AICI3 *6H2O und 14,64 g Fumarsäure (AhLinkerverhältnis = 1 ,7 mol/mol) werden in einem Glaskolben in 550 ml DMF suspendiert (Feststoffgehalt = 0,058 g/g) und 17 h unter Rückfluss (130°C) gerührt. Der entstandene Feststoff wird abfiltriert und mit 3 x 100 ml Aceton und 2 x 100 ml Methanol gewaschen. Anschließend wird die Substanz im Vakuumtrockenschrank bei 100°C 16 h getrocknet. Es werden 1 1 ,4g eines weißen Vorprodukts erhalten. Die N2-Oberfläche wird mit 1271 m2/g (Langmuir) bestimmt.Example 3 Preparation of a pure Al fumarate MOF 17.91 g AICI 3 * 6H 2 O and 14.64 g fumaric acid (Ah linker ratio = 1.7 mol / mol) are suspended in 550 ml DMF in a glass flask (solids content = 0.058 g / g) and stirred for 17 h at reflux (130 ° C). The resulting solid is filtered off and washed with 3 x 100 ml of acetone and 2 x 100 ml of methanol. The substance is then dried in a vacuum oven at 100 ° C for 16 h. There are obtained 1 1, 4g of a white precursor. The N 2 surface is determined to be 1271 m 2 / g (Langmuir).
Beispiel 4 Herstellung eines reinen AI-Fumarat-MOFsExample 4 Preparation of a pure Al fumarate MOF
26,9 g AICl3*6H2O und 15,4 g Fumarsäure (AhLinkerverhältnis = 1 ,2 mol/mol) werden in einem Glaskolben in 550 ml DMF suspendiert (Feststoffgehalt = 0,078 g/g) und 96 h unter Rückfluss (130°C) gerührt. Der entstandene Feststoff wird abfiltriert und mit 3 x 100 ml Aceton und 3 x 100 ml Methanol gewaschen. Anschließend wird die Substanz im Vakuumtrockenschrank bei 100°C 16 h getrocknet. Es werden 18,4g eines weißen Vorprodukts erhalten. Die N2-Oberfläche wird mit 1272 m2/g (Langmuir) bestimmt. 26.9 g AICl3 * 6H 2 O and 15.4 g fumaric acid (AhLinker ratio = 1.2 mol / mol) are suspended in a glass flask in 550 ml DMF (solids content = 0.078 g / g) and 96 h under reflux (130 ° C) stirred. The resulting solid is filtered off and washed with 3 x 100 ml of acetone and 3 x 100 ml of methanol. The substance is then dried in a vacuum oven at 100 ° C for 16 h. There are obtained 18.4 g of a white precursor. The N 2 surface is determined to be 1272 m 2 / g (Langmuir).
Beispiel 5 Wasserstoff-Isothermen bei 77 KExample 5 Hydrogen isotherms at 77K
In Fig. 2 ist die H2-Aufnahme des erfindungsgemäßen MOF dargestellt. Die Messung erfolgt an einem kommerziell erhältlichen Gerät der Fa. Quantachrome mit der Be- Zeichnung Autosorb-1. Die Messtemperatur liegt bei 77.4 K. Die Probe wird vor der Messung 4 h bei Raumtemperatur und anschließend weitere 4 h bei 200°C im Vakuum vorbehandelt.FIG. 2 shows the H 2 uptake of the MOF according to the invention. The measurement is carried out on a commercially available device from the company Quantachrome with the designation Autosorb-1. The measuring temperature is 77.4 K. The sample is pretreated for 4 hours at room temperature before the measurement and then for a further 4 hours at 200 ° C. in vacuo.
Fig. 2 zeigt die Wasserstoffkapazität K (cc/g STP) als Funktion des relativen Drucks p/po (Po = 94632,4 Torr).Fig. 2 shows the hydrogen capacity K (cc / g STP) as a function of the relative pressure p / po (Po = 94632.4 Torr).
Beispiel 6 Wasserstoff-Isothermen bei 77 KExample 6 Hydrogen isotherms at 77K
In Fig. 3 ist die H2-Aufnahme für den Al-Fumarat MOF dargestellt. Die Messtemperatur liegt bei 77.4 K. Die Proben werden vor der Messung jeweils 4 h bei Raumtemperatur und anschließend weitere 4 h bei 200°C im Vakuum vorbehandelt.FIG. 3 shows the H 2 uptake for the Al fumarate MOF. The measurement temperature is 77.4 K. The samples are each pretreated for 4 hours at room temperature and then for a further 4 hours at 200 ° C. in vacuum before the measurement.
Es ist die Wasserstoffaufnahme (g/l) als Funktion des absoluten Drucks p (bar) dargestellt.The hydrogen uptake (g / l) is shown as a function of the absolute pressure p (bar).
Beispiel 7 Eignung für die CO2 -TrennungenExample 7 Suitability for CO 2 separations
Es werden bei 42°C Reinstoff isothermen von CO2, CO und Methan (21 °C) an dem Material aus Beispiel 1 aufgenommen (Fig. 4). Die starke Differenz zwischen der CO und CO2-Aufnahme zeigt, dass dieses Material prinzipiell eine gute Selektivität für die Trennaufgaben CO2/Methan und CO2/CO besitzt.At 42 ° C., pure substance isotherms of CO 2 , CO and methane (21 ° C.) are absorbed on the material from Example 1 (FIG. 4). The strong difference between the CO and CO 2 uptake shows that this material has in principle a good selectivity for the separation tasks CO 2 / methane and CO 2 / CO.
In Fig. 4 ist die absorbierte Menge A (mg/g) als Funktion des absoluten Drucks p (mbar) dargestellt. Hierbei entsprechen die Kurven 1 , 2 und 3 den Gasen CO2, Methan und CO. In Fig. 4, the absorbed amount A (mg / g) is shown as a function of the absolute pressure p (mbar). Curves 1, 2 and 3 correspond to the gases CO 2 , methane and CO.

Claims

Patentansprüche claims
1. Poröses metallorganisches Gerüstmaterial gebildet aus Al'" Ionen, an die koordi- nativ Fumarationen unter Ausbildung einer Gerüststruktur gebunden sind.1. Porous organometallic framework formed from Al 'ions to which coordinate fumarations are bonded to form a framework structure.
2. Gerüstmaterial nach Anspruch 1 , dadurch gekennzeichnet, dass das Röntgen- diffraktogramm (XRD) des Gerüstmaterials im Bereich von 8° < 2Θ < 12° einen Basisreflex aufweist.2. Framework according to claim 1, characterized in that the X-ray diffractogram (XRD) of the framework material in the range of 8 ° <2Θ <12 ° has a base reflection.
3. Gerüstmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das ge- rüstmaterial eine orthorhombische eindimensionale Kanalstruktur aufweist.3. Framework material according to claim 1 or 2, characterized in that the framework material has an orthorhombic one-dimensional channel structure.
4. Gerüstmaterial nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Gerüstmaterial als Pulver eine spezifische Oberfläche bestimmt nach4. Framework material according to one of claims 1 to 3, characterized in that the framework material determines a specific surface as a powder
Langmuir durch N2 Adsorption bei 77 K von mindestens 1000 m2/g aufweist.Langmuir by N 2 adsorption at 77 K of at least 1000 m 2 / g.
5. Formkörper enthaltend ein poröses metallorganisches Gerüstmaterial nach einem der Ansprüche 1 bis 4.5. Shaped body containing a porous organometallic framework material according to one of claims 1 to 4.
6. Verfahren zur Herstellung eines porösen metallorganischen Gerüstmaterials nach einem der Ansprüche 1 bis 3 den Schritt enthaltend,6. A process for producing a porous organometallic framework according to any one of claims 1 to 3 comprising the step,
Umsetzung eines Reaktionsgemisches enthaltend mindestens eine Aluminium- Verbindung und Fumarsäure oder ein Salz davon in Gegenwart eines organischen Lösemittels bei einer vorgegebenen Temperatur und einem vorgegebenen Druck.Reaction of a reaction mixture comprising at least one aluminum compound and fumaric acid or a salt thereof in the presence of an organic solvent at a predetermined temperature and a predetermined pressure.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die Aluminiumver- bindung das Hydrat eines Aluminiumsalzes ist.7. The method according to claim 6, characterized in that the aluminum compound is the hydrate of an aluminum salt.
8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass die vorgegebene Temperatur im Bereich von 100 bis 200 °C liegt.8. The method according to claim 6 or 7, characterized in that the predetermined temperature is in the range of 100 to 200 ° C.
9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass der vorgegebene Druck im Bereich von 1 bis 16 bar (absolut) liegt.9. The method according to any one of claims 6 to 8, characterized in that the predetermined pressure in the range of 1 to 16 bar (absolute).
10. Verfahren nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass das molare Verhältnis Al'" zu Fumarsäure oder deren Salz im Bereich von 0,3 : 1 bis 1 ,7 : 1 liegt. 10. The method according to any one of claims 6 to 9, characterized in that the molar ratio Al '"to fumaric acid or its salt in the range of 0.3: 1 to 1, 7: 1.
1 1. Verwendung eines porösen metallorganischen Gerüstmaterials nach einem der Ansprüche 1 bis 4 oder eines Formkörpers nach Anspruch 5 zur Aufnahme eines Stoffes zu dessen Speicherung oder kontrollierten Abgabe.1 1. Use of a porous organometallic framework material according to any one of claims 1 to 4 or a shaped article according to claim 5 for receiving a substance for its storage or controlled release.
12. Verwendung nach Anspruch 11 , dadurch gekennzeichnet, dass der Stoff Methan oder Wasserstoff ist.12. Use according to claim 11, characterized in that the substance is methane or hydrogen.
13. Verwendung eines porösen metallorganischen Gerüstmaterials nach einem der Ansprüche 1 bis 4 oder eines Formkörpers nach Anspruch 5 zur Aufnahme eines13. Use of a porous organometallic framework according to any one of claims 1 to 4 or a shaped body according to claim 5 for receiving a
Stoffes zu dessen Abtrennung.Substance for its separation.
15. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass der Stoff Kohlendioxid ist.15. The method according to claim 13, characterized in that the substance is carbon dioxide.
16. Verwendung eines porösen metallorganischen Gerüstmaterials nach einem der Ansprüche 1 bis 4 oder eines Formkörpers nach Anspruch 5 zur Aufnahme eines Stoffes zu dessen chemischen Umsetzung oder als Träger. 16. Use of a porous organometallic framework according to any one of claims 1 to 4 or a shaped body according to claim 5 for receiving a substance for its chemical reaction or as a carrier.
EP07728034A 2006-04-18 2007-04-12 Organometallic aluminum fumarate backbone material Ceased EP2010315A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07728034A EP2010315A2 (en) 2006-04-18 2007-04-12 Organometallic aluminum fumarate backbone material

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06112713 2006-04-18
PCT/EP2007/053567 WO2007118841A2 (en) 2006-04-18 2007-04-12 Organometallic aluminum fumarate backbone material
EP07728034A EP2010315A2 (en) 2006-04-18 2007-04-12 Organometallic aluminum fumarate backbone material

Publications (1)

Publication Number Publication Date
EP2010315A2 true EP2010315A2 (en) 2009-01-07

Family

ID=38421790

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07728034A Ceased EP2010315A2 (en) 2006-04-18 2007-04-12 Organometallic aluminum fumarate backbone material

Country Status (6)

Country Link
US (3) US20090092818A1 (en)
EP (1) EP2010315A2 (en)
JP (1) JP5150617B2 (en)
KR (2) KR101493529B1 (en)
CN (2) CN101421183A (en)
WO (1) WO2007118841A2 (en)

Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101680600A (en) * 2007-04-05 2010-03-24 巴斯夫欧洲公司 Gas pressure container comprising a mixture containing an organometallic skeletal material, and a pcm device
ES2397231T3 (en) * 2007-04-24 2013-03-05 Basf Se Organometallic structural materials, with a hexagonal and trigonal structure, based on aluminum, iron or chromium, as well as a dicarboxylic acid
ES2402323T3 (en) * 2007-05-21 2013-04-30 Basf Se Aluminum amino carboxylates as porous organometallic structural materials
WO2009007267A1 (en) * 2007-07-10 2009-01-15 Basf Se Process for the separation of unbranched hydrocarbons from their branched isomers
EP2190662B1 (en) * 2007-09-25 2018-12-26 The Regents of The University of California Edible and biocompatible metal-organic frameworks
JP2011509825A (en) * 2008-01-24 2011-03-31 ビーエーエスエフ ソシエタス・ヨーロピア Porous organometallic framework materials as desiccants
ES2378441T3 (en) * 2008-03-17 2012-04-12 Basf Se Use of porous organometallic structural materials based on formate for methane storage
FR2938540B1 (en) 2008-11-18 2017-08-11 Centre Nat Rech Scient METHOD FOR THE HYDROTHERMAL PREPARATION OF CRYSTALLIZED POROUS ALUMINUM CARBOXYLATES OF THE "METAL-ORGANIC FRAMEWORK" TYPE
FR2938539B1 (en) 2008-11-18 2012-12-21 Centre Nat Rech Scient PROCESS FOR THE PREPARATION OF AROMATIC AROMATIC AZOCARBOXYLATES OF POROUS AND CRYSTALLIZED ALUMINUM OF THE "METAL-ORGANIC FRAMEWORK" TYPE
DE202009017307U1 (en) * 2009-12-18 2010-03-18 Basf Se Use of at least one porous organometallic framework (MOF) to reduce the methane gas content and to increase the overall gas yield in animal feed
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
CN101920213B (en) * 2010-07-23 2012-09-19 中环（中国）工程有限公司 Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof
CA2812294A1 (en) 2010-09-27 2012-06-21 The Regents Of The University Of California Conductive open frameworks
MX2013002464A (en) * 2010-09-30 2013-06-11 Basf Se Process for preparing porous metal-organic frameworks based on aluminum fumarate.
US8524932B2 (en) 2010-09-30 2013-09-03 Basf Se Process for preparing porous metal-organic frameworks based on aluminum fumarate
US8758482B2 (en) * 2011-05-02 2014-06-24 Rutgers, The State University Of New Jersey Methods and compositions for removing carbon dioxide from a gaseous mixture
CN102183867B (en) * 2011-05-21 2012-10-10 辽宁省颅面复原技术重点实验室 Three-dimension Pan/Tilt/Zoom (PTZ) camera
GB201207208D0 (en) * 2012-04-25 2012-06-06 Johnson Matthey Plc Compound and method of manufacture
GB201215693D0 (en) * 2012-09-03 2012-10-17 Univ Liverpool Metal-organic framework
EP3049185B1 (en) * 2013-09-23 2019-12-11 Basf Se Process for the recovery of components forming a metal-organic framework material
US10035127B2 (en) 2013-11-04 2018-07-31 The Regents Of The University Of California Metal-organic frameworks with a high density of highly charged exposed metal cation sites
GB201414114D0 (en) * 2013-11-26 2014-09-24 Texas A & M Univ Sys Aluminium metal organic framework materials
ES2768680T3 (en) 2014-02-19 2020-06-23 Univ California Organometallic frames that have resistance to acids, solvents, and thermal
WO2015142944A2 (en) 2014-03-18 2015-09-24 The Regents Of The University Of California Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks
WO2015195179A2 (en) 2014-03-28 2015-12-23 The Regents Of The University Of California Metal organic frameworks comprising a plurality of sbus with different metal ions and/or a plurality of organic linking ligands with different functional groups.
DE102014215568A1 (en) 2014-08-06 2016-02-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for producing an adsorbent from organometallic frameworks (MOF)
WO2016025624A1 (en) * 2014-08-12 2016-02-18 Northwestern University Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts
CN104445079B (en) * 2014-11-28 2017-02-22 中国科学院过程工程研究所 Homogeneous-phase multi-element porous oxide material, preparation method and application thereof
US10118877B2 (en) 2014-12-03 2018-11-06 The Regents Of The University Of California Metal-organic frameworks for aromatic hydrocarbon separations
US10058855B2 (en) 2015-05-14 2018-08-28 The Regents Of The University Of California Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons
AU2016289276B2 (en) * 2015-07-08 2020-11-05 Commonwealth Scientific And Industrial Research Organisation Composition and system for gas storage
CN105036099A (en) * 2015-07-15 2015-11-11 李亚丰 Tetragonal phase zirconium dioxide with carbon stability under normal temperature and pressure and preparation method
CN107921409B (en) 2015-10-05 2021-01-12 韩国生产技术研究院 Method for preparing moisture-absorbing composition, moisture-absorbing composition prepared by the same and moisture-absorbing composition for surface coating
US10737239B2 (en) * 2015-11-27 2020-08-11 Basf Se Ultrafast high space-time-yield synthesis of metal-organic frameworks
KR20180088422A (en) 2015-11-27 2018-08-03 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 The woven covalent organic framework
JP2018538282A (en) 2015-11-27 2018-12-27 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア Zeolite-like imidazolate structure
GB201615268D0 (en) 2016-09-08 2016-10-26 Univ I Oslo And Christian-Albrechts-Universit�T Zu Kiel Process
GB201615270D0 (en) 2016-09-08 2016-10-26 Univ Oslo Process
KR101950316B1 (en) * 2016-10-27 2019-02-20 한국생산기술연구원 Metal doped organic-inorganic nanoporous materials adsorbent of water and method for manufacturing of adsorbent of water using the same
CN107376863B (en) * 2017-08-30 2020-04-24 河南师范大学 Preparation method of AlFu @ CB composite adsorption material for adsorption and purification treatment of high-concentration fluorine-containing wastewater
CN108715457A (en) * 2018-06-21 2018-10-30 福州大学 Based on MOF template controlledly synthesis nano structure of zinc oxide gas sensors
SG11202004237PA (en) 2018-08-16 2020-06-29 Commw Scient Ind Res Org Metal organic framework based water capture apparatus
CN109160824B (en) * 2018-08-21 2021-02-02 武汉摩尔安科技有限公司 Ceramic porous material based on MOFs (metal-organic frameworks) and preparation method thereof
US11045785B2 (en) 2018-11-05 2021-06-29 Industrial Technology Research Institute Metal-organic framework, method for preparing the same, and adsorption device employing the same
EP3653283A1 (en) * 2018-11-15 2020-05-20 Basf Se Process for conditioning metal-organic frameworks by means of membrane filtration
CN109987585B (en) * 2019-04-28 2022-04-22 江南大学 Preparation method of ultrathin hydroxide nanosheet for producing oxygen by electrolyzing water
CN110364716B (en) * 2019-07-24 2021-01-29 淮安新能源材料技术研究院 Magnesium-based MOF spherical magnesium oxide coated lithium ion battery ternary positive electrode material and preparation method thereof
EP4188993A1 (en) 2020-08-03 2023-06-07 Basf Se A polyester molding comprising a metal-organic framework having a low outgassing of volatile organic compounds
CN113336955B (en) * 2021-01-27 2022-12-27 重庆理工大学 Hollow rare earth-based MOFs material based on solvothermal method
CN112755965B (en) * 2021-02-25 2023-07-21 北京工业大学 Preparation method of composite dehumidification adsorbent paper sheet made of MOF material and lithium chloride
JP7277801B2 (en) 2021-03-15 2023-05-19 ダイキン工業株式会社 adsorption system
WO2023002141A1 (en) 2021-07-23 2023-01-26 Centre National De La Recherche Scientifique Method for preparing a crystalline porous aluminum tetracarboxylate of mof type, and uses thereof
CN114405063B (en) * 2021-11-12 2023-02-24 河北大学 Method for enriching and purifying diosmetin from dandelion on line
CN115212652A (en) * 2022-07-01 2022-10-21 北京师范大学 Argil water filtration material containing metal organic framework derived carbon and argil water purifier
CN115634666B (en) * 2022-11-09 2024-04-05 合肥工业大学 Method for preparing adsorbent by taking fly ash as raw material and application of adsorbent in separation of methane and nitrogen
CN116396486B (en) * 2023-01-04 2023-12-22 华南理工大学 Aluminum-based metal organic framework material for preferentially adsorbing argon and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008062034A1 (en) * 2006-11-24 2008-05-29 Basf Se Method for separating gases using a porous metal organic framework material
WO2008122542A2 (en) * 2007-04-05 2008-10-16 Basf Se Mixture containing an organometallic skeletal material, and pcm device

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3231498A1 (en) 1982-08-25 1984-03-01 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING HARD, BREAK-RESISTANT CATALYSTS FROM ZEOLITE POWDER
IT1187661B (en) 1985-04-23 1987-12-23 Enichem Sintesi HIGH MECHANICAL RESISTANCE SILICON AND TITANIUM BASED CATALYST
GB8906726D0 (en) 1989-03-23 1989-05-10 Shell Int Research Titania extrudates
JPH0337156A (en) 1989-07-03 1991-02-18 Sumitomo Metal Mining Co Ltd Formed and calcined zeolite and its production
US5182410A (en) * 1990-12-14 1993-01-26 Aluminum Company Of America Organo-aluminum hydroxide compounds
EP0592050B1 (en) 1992-10-08 1996-04-10 Shell Internationale Researchmaatschappij B.V. Process for extruding crystalline aluminosilicates
US5378671A (en) 1993-06-03 1995-01-03 Mobil Oil Corp. Method for preparing catalysts comprising zeolites
ES2139187T3 (en) 1994-01-12 2000-02-01 Du Pont MICROPOROUS COMPOSITE MATERIAL OF PERFORMED POLYMER EXCHANGED ION AND METAL OXIDE OBTAINED BY A SUN-GEL.
JPH1066949A (en) * 1996-08-28 1998-03-10 Osaka Gas Co Ltd Decomposing method of organic metallic complex
JP3985114B2 (en) * 1998-10-05 2007-10-03 大阪瓦斯株式会社 Novel three-dimensional organometallic complex and gas adsorbent
US20030078311A1 (en) 2001-10-19 2003-04-24 Ulrich Muller Process for the alkoxylation of organic compounds in the presence of novel framework materials
US6929679B2 (en) 2002-02-01 2005-08-16 Basf Aktiengesellschaft Method of storing, uptaking, releasing of gases by novel framework materials
US6666666B1 (en) 2002-05-28 2003-12-23 Denis Gilbert Multi-chamber positive displacement fluid device
US6624318B1 (en) 2002-05-30 2003-09-23 Basf Aktiengesellschaft Process for the epoxidation of an organic compound with oxygen or an oxygen-delivering compounds using catalysts containing metal-organic frame-work materials
US6893564B2 (en) 2002-05-30 2005-05-17 Basf Aktiengesellschaft Shaped bodies containing metal-organic frameworks
US6628229B1 (en) 2002-08-01 2003-09-30 Rosemount Inc. Stabilization of oscillators in a radar level transmitter
US7008607B2 (en) 2002-10-25 2006-03-07 Basf Aktiengesellschaft Process for preparing hydrogen peroxide from the elements
US6617467B1 (en) 2002-10-25 2003-09-09 Basf Aktiengesellschaft Process for producing polyalkylene carbonates
US7309380B2 (en) 2003-06-30 2007-12-18 Basf Aktiengesellschaft Gas storage system
US20050004404A1 (en) 2003-07-03 2005-01-06 Basf Akiengesellschaft Process for the alkoxylation of monools in the presence of metallo-organic framework materials
DE10355087A1 (en) 2003-11-24 2005-06-09 Basf Ag Process for the electrochemical preparation of a crystalline porous organometallic framework
DE102004061238A1 (en) 2004-12-20 2006-06-22 Basf Ag Method for the enrichment of methane in methane containing gas mixtures comprises contacting the gas mixture with at least a sorbent containing a porous metal-organic structure material
DE102005000938A1 (en) 2005-01-07 2006-07-20 Basf Ag Adsorptive recovery of xenon from krypton-xenon mixed gas
US7343747B2 (en) 2005-02-23 2008-03-18 Basf Aktiengesellschaft Metal-organic framework materials for gaseous hydrocarbon storage
DE102005012087A1 (en) 2005-03-16 2006-09-21 Basf Ag Liquid absorption by organometallic frameworks
DE102005022844A1 (en) 2005-05-18 2006-11-23 Basf Ag Separation of odors from gases
DE102005039623A1 (en) * 2005-08-22 2007-03-01 Basf Ag Process for the preparation of organometallic frameworks Main groups containing metal ions
DE102005053430A1 (en) * 2005-11-09 2007-05-16 Basf Ag Doped organometallic frameworks
WO2007113118A1 (en) * 2006-03-29 2007-10-11 Basf Se Method for commercially obtaining propene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008062034A1 (en) * 2006-11-24 2008-05-29 Basf Se Method for separating gases using a porous metal organic framework material
WO2008122542A2 (en) * 2007-04-05 2008-10-16 Basf Se Mixture containing an organometallic skeletal material, and pcm device

Also Published As

Publication number Publication date
KR20080112349A (en) 2008-12-24
JP2009534348A (en) 2009-09-24
JP5150617B2 (en) 2013-02-20
CN101448568A (en) 2009-06-03
US8734652B2 (en) 2014-05-27
US20090092818A1 (en) 2009-04-09
KR20080112382A (en) 2008-12-24
WO2007118841A3 (en) 2008-01-03
US20120167761A1 (en) 2012-07-05
US8518264B2 (en) 2013-08-27
US20130210620A1 (en) 2013-08-15
CN101421183A (en) 2009-04-29
WO2007118841A2 (en) 2007-10-25
KR101493529B1 (en) 2015-02-13

Similar Documents

Publication Publication Date Title
EP2010315A2 (en) Organometallic aluminum fumarate backbone material
EP2155390B1 (en) New organometallic framework materials based on aluminum, iron, and chromium
EP2089153B1 (en) Aluminum naphthalenedicarboxylate as a porous organometallic framework material
EP2004589B1 (en) Process for preparing porous metal-organic framework materials
EP1917228B1 (en) Mesoporous metal-organic framework
EP2089157B1 (en) Magnesium butylisophthalate as a porous metal organic framework material
EP2150338B1 (en) Aluminum amino carobxylates as porous organometallic skeleton materials
EP1922299B1 (en) Method for producing organometallic framework materials containing main group metal ions
WO2007118874A1 (en) Metal-organic zirconium-based framework materials
WO2007118888A1 (en) Methods for producing metal-organic framework materials containing metals of subgroup iv
EP1954395A1 (en) Organometallic framework materials of transition group iii

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081118

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17Q First examination report despatched

Effective date: 20090508

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20111014