EP2142297A1 - Matériaux en réseau organométallique poreux chargés de composants métalliques catalyseur - Google Patents

Matériaux en réseau organométallique poreux chargés de composants métalliques catalyseur

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Publication number
EP2142297A1
EP2142297A1 EP08736411A EP08736411A EP2142297A1 EP 2142297 A1 EP2142297 A1 EP 2142297A1 EP 08736411 A EP08736411 A EP 08736411A EP 08736411 A EP08736411 A EP 08736411A EP 2142297 A1 EP2142297 A1 EP 2142297A1
Authority
EP
European Patent Office
Prior art keywords
catalyst metal
acid
catalyst
porous
metal component
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.)
Withdrawn
Application number
EP08736411A
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German (de)
English (en)
Inventor
Markus Schubert
Stefan Kotrel
Ulrich Müller
Christoph Kiener
Thilo Hahn
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08736411A priority Critical patent/EP2142297A1/fr
Publication of EP2142297A1 publication Critical patent/EP2142297A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B01J35/30—
    • B01J35/393—
    • B01J35/617—
    • B01J35/618—

Definitions

  • the present invention relates to porous organometallic frameworks and porous metal oxides formed therefrom which are loaded with catalyst metal components, and to their preparation and use.
  • catalysts often consist of a carrier material and a catalytically active species, such as elemental metal or a metal oxide.
  • Suitable support materials are, for example, activated carbon, metal oxides, zeolites and porous organometallic frameworks.
  • MOF-5 zinc terephthalate, one of the best-known organometallic frameworks.
  • PVD or CVD physical and chemical vacuum deposition
  • WO-A 03/101975 a catalyst is proposed for the epoxidation in which MOF-5 is impregnated with a metal salt, wherein the metal is Ag + .
  • conversion of the metal is not required for the reaction.
  • the object is achieved by a method for producing a porous organometallic framework material loaded with a catalyst metal component comprising the steps
  • the object is further achieved by a porous organometallic framework material loaded with a catalyst metal component obtainable from the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component.
  • porous organometallic framework material can be converted into a porous metal oxide.
  • the object is therefore likewise achieved by a method for producing a porous metal oxide loaded with a catalyst metal component comprising the steps
  • the object is achieved by a porous metal oxide loaded with a catalyst metal component obtainable from the process according to the invention for the preparation of a catalyst metal component loaded with a porous metal oxide.
  • the organometallic framework can be transferred in the present invention in the charged state into the corresponding metal oxide by the catalyst metal-laden with the metal-organometallic porous material is heated above its complete decomposition temperature in an oxidizing atmosphere.
  • step (a) of the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component an organometallic framework material comprising at least one of at least one metal ion - A -
  • the at least one metal ion and the catalyst metal ion derived from different metals and the at least one metal ion is selected from the group of metals consisting of groups 2, 3, 4, 13 of the Periodic Table of the Elements and the lanthanides.
  • the organometallic frameworks according to the present invention contain pores, in particular micropores and / or mesopores.
  • Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described in Pure & Applied Chem. 57 (1985), 603-619 , in particular on page 606.
  • 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 DIN 66131 and / or DIN 66134.
  • the specific surface area - calculated according to the Langmuir model (DIN 66131, 66134) for an organometallic framework in powder form is more than 5 m 2 / g, more preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, more preferably more than 500 m 2 / g, even more preferably more than 1000 m 2 / g and particularly preferably more than 1500 m 2 / g.
  • Moldings of organometallic frameworks may have a lower specific surface area; but preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, even more preferably more than 500 m 2 / g.
  • the metal component in the framework of the present invention is selected from Groups 2, 3, 4, 13 and the lanthanides. Accordingly, suitable metals are Be, Mg, Ca, Sr, Ba, Sc, Y, Lu, Ti, Zr, Hf, Al, Ga, In, Tl and Ln, where Ln is lanthanide.
  • Lanthanides are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.
  • At least bidentate organic compound refers to an organic compound containing at least one functional group capable of having at least two coordinative bonds to a given metal ion, and / or to two or more, preferably two, metal atoms each having a coordinative bond train.
  • Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: -CO 2 H, -CS 2 H, -NO 2 , -B (OH) 2 , -SO 3 H, - Si (OH) 3, -Ge (OH) 3, -Sn (OH) 3, -Si (SH) 4, - Ge (SH) 4, -Sn (SH) 3, -PO 3 H, 3 H -AsO , -AsO 4 H, -P (SH) 3 , -As (SH) 3 , -CH (RSH) 2 , -C (RSH) 3 -CH (RNH 2 ), -C (RNH 2 ) 3 , -CH (ROH) 2 , -C (ROH) 3 , -CH (RCN) 2 , -C (RCN) 3 where, for example, R preferably represents an alkylene group having 1, 2, 3, 4 or 5 carbon atoms
  • functional groups are to be mentioned in which the abovementioned radical R is absent.
  • R is absent.
  • functional groups are, inter alia, -CH (SH) 2, -C (SH) 3, -CH (NH 2) 2, - C (NH 2) 3, -CH (OH) 2, -C (OH) 3, -CH (CN) 2 or -C (CN) 3 TO call.
  • the at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinative bond and the preparation of the framework.
  • the organic compounds containing the at least two functional groups derived from a saturated or unsaturated aliphatic compound o- of an aromatic compound or an aliphatic as well as aromatic compound are preferred.
  • the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic or the aliphatic portion of the aliphatic as well as aromatic compound 1 to 15, more preferably 1 to 14, more preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 1 1 and especially preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both the aromatic and the aliphatic compound may have one or more nuclei, for example two, three, four or five nuclei, wherein the nuclei may be present in separate and / or at least two nuclei in condensed form , Most preferably, the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred. Independently of each other, furthermore, each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S.
  • the aromatic compound or the aromatic part of the both aromatic and aliphatic compounds contains one or two C ⁇ cores, the two being present either separately or in condensed form.
  • benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • the at least bidentate organic compound is particularly preferably derived from a di-, tri- or tetracarboxylic acid.
  • the term "derived" in the context of the present invention means that the at least bidentate organic compound can be present in the framework material in partially deprotonated or completely deprotonated form or as sulfur analogues. Furthermore, the at least bidentate organic compound may contain further substituents such as -OH, -NH 2 , -OCH 3 , -CH 3 , -NH (CH 3 ), -N (CH 3 ) 2 , -CN and halides.
  • dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid bonic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1, 3 Butadiene-1, 4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methyl-quinoline-3,4-dicar
  • Tricarboxylic acids such as
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
  • monocarboxylic dicarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicerate dicarboxylic acids, dicercaric tricarboxylic acids, dicercaric tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic acids.
  • nary tetracarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicerate dicarboxylic acids, dicercaric tricarboxylic acids, dicercaric te
  • Suitable heteroatoms are, for example, N, O, S, B, P, Si, Al, preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or To name alkoxy group.
  • the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
  • Preferred heterocycles as at least bidentate organic compounds in which a coordinate bond via the ring heteroatoms takes place are the following substituted or unsubstituted ring systems:
  • Suitable heteroatoms are, for example, N, O, S, B, P. Preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group ,
  • Particularly preferred at least bidentate organic compounds are imidazolates, such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), campherdicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TEDA), naphthalenedicarboxylic acids ( NDC), biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazine dicarboxylic acids such as 2,5-pyrazine dicarboxylic acid, bipyridine dicarboxylic acids such as 2,2'-bipyridine dicarboxylic acids such as 2,2'-bipyridine-5,5'-dicarboxylic acid, Benzene tricarboxylic acids such as 1,3,3,1,2,4-benzenetricar
  • the organometallic framework material may also comprise one or more monodentate ligands and / or one or more at least bidentate ligands which are not derived from a di-, tri- or tetracarboxylic acid.
  • the conventional method for producing the organometallic frameworks as described for example in US 5,648,508, they can also be prepared by electrochemical means.
  • DE-A 103 55 087 as referred to WO-A 2005/049892.
  • the organometallic frameworks prepared in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases.
  • inventively loaded as well as the non-loaded organometallic framework material are present in powdered or crystalline form. This can be used as such. This is preferably done as bulk material, in particular in a fixed bed.
  • the loaded organometallic framework material can be converted into a shaped body.
  • Preferred methods here are the extrusion or tableting.
  • other materials such as binders, lubricants or other additives may be added to the organometallic framework.
  • pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
  • the framework material can then be further processed according to the method described above to give a shaped body.
  • Kneading and molding may be done according to any suitable method as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Volume 2, pp. 313 et seq. (1972), the contents of which are incorporated by reference in the context of the present application in its entirety ,
  • kneading and / or shaping by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, coextrusion, foaming, spinning, coating, granulation, preferably spray granulation, spraying, spray drying may be preferred or a combination of two or more of these methods.
  • pellets and / or tablets are produced.
  • Kneading and / or shaping may be carried out at elevated temperatures, for example in the range from room temperature to 300 ° C. and / or at elevated pressure, for example in the range from atmospheric pressure to several 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.
  • clay minerals as described for example in JP 03-037156 A, for example montmorillonite, kaolin, bentonite, halloysite, Dickit, Nacrit and anauxite, alkoxysilanes, as described for example in EP 0 102 544 B1
  • tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane
  • alkoxy titanates for example tetraalkoxytitanates such as tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy poxytitanat, tetrabutoxytitanate, or, for example, trialkoxyt
  • an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative 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 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 as a mixture with water and / or at least one of said monohydric alcohols be 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, which generally takes place at a temperature in the range from 25 to 300 ° C., preferably in the range from 50 to 300 ° C. and more preferably in the range from 100 to 300 0 C is performed.
  • at least one drying which generally takes place at a temperature in the range from 25 to 300 ° C., preferably in the range from 50 to 300 ° C. and more preferably in the range from 100 to 300 0 C is performed.
  • At least one of the compounds added as additives is at least partially removed from the shaped body.
  • step (a) of the process according to the invention for producing a porous metal organic framework material loaded with a catalyst metal component it is brought into contact with an aqueous solution containing a catalyst metal ion corresponding to the catalyst metal component.
  • the aqueous solution contains, in addition to the cation, another anion.
  • Preferred anions are nitrates, carbonates, chlorides, acetylacetonates, acetates, formates or oxalates.
  • Such salts can also be used in their hydrate form.
  • rhenium come perrhenic acid, ammonium perrhenate or methyltrioxorhenium in question.
  • the aqueous solution preferably has a pH of less than 9, more preferably less than 7, in particular less than 4.
  • the bringing into contact is usually carried out by impregnation.
  • the porous organometallic framework material is impregnated with the aqueous solution, this being a dip or a dry impregnation.
  • the amount of the aqueous solution is smaller than or equal to the liquid receiving volume of the organometallic skeleton.
  • the aqueous solution is used in particular significant excess.
  • the dry impregnation is preferred.
  • the impregnation can be repeated, wherein a drying and / or calcination can take place between the individual impregnation processes. Due to the different impregnation processes, different metal ions can also be introduced.
  • An aqueous solution may also contain multiple catalyst metal ions. To simplify matters, the term metal ion in the singular is also used here.
  • step (b) of the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component a chemical conversion of the catalyst metal ion into the catalyst metal component takes place.
  • this step may be preceded by a separation step and a drying step.
  • the catalyst metal component is preferably elemental metal, ie metal in the oxidation state 0 or a metal oxide. Accordingly, the metal ion is subjected to reduction, oxidation or chemical conversion to obtain the oxidation state. Preference is given to reduction and oxidation. In particular, the reduction is preferred.
  • the chemical conversion is conveniently carried out by exposing the organometallic framework, which has been brought into contact with the aqueous solution, to a reducing or oxygen-providing atmosphere.
  • a typical reducing atmosphere would be a hydrogen atmosphere.
  • a typical oxygen-providing atmosphere would be pure oxygen or preferably an oxygen-containing gas, in particular air.
  • the metal of the catalyst metal component is preferably selected from the group consisting of Cu, Ag, Au, Pt, Pd, Rh, Ru, Ir, Re, Fe, Co and Ni. More preferred are Pt, Pd, Rh, Ru, Co and Ni.
  • step (b) of the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component is preferably carried out at elevated temperature.
  • the temperature is in the range of 100 0 C to 400 0 C. More preferred is a range from 120 0 C to 300 0 C, in particular 125 0 C to 200 0 C.
  • a passivation step may optionally be followed to make the porous organometallic framework loaded with a catalyst metal component storable and transportable.
  • the passivation is activated shortly before the material is used, for example in catalysis, by reversing the passivation reaction.
  • a typical passivation, especially in the case of an activation step by reduction, is gentle oxidation. In this case, for example, also air can be used.
  • comparatively low temperatures are chosen here.
  • the temperature is at the Passivation less than 100 0 C, but above room temperature (25 0 C), more preferably less than 50 0 C.
  • porous organometallic framework is loaded with a catalyst metal component, it can be converted to the corresponding porous metal oxide. This presupposes that the framework material is converted into the corresponding porous metal oxide over its complete decomposition temperature in an oxygen-supplying atmosphere.
  • the framework material loaded with the catalyst metal ion may also be directly, i. without generating the catalyst metal component, are converted to a metal oxide.
  • a step (a 1 ) the process according to the invention for producing a porous metal oxide loaded with a catalyst metal component provides for heating the charged porous organometallic framework material.
  • the material may be present in a dispersion or as a dry solid.
  • the organometallic framework material can be present as a powder or as a shaped body or both.
  • the heating is carried out with a porous organometallic framework in the form of a powder.
  • the heating can be carried out by methods known to those skilled in the art.
  • the heating is carried out in a suitable furnace, such as a muffle furnace or rotary kiln.
  • a suitable furnace such as a muffle furnace or rotary kiln.
  • a suitable atmosphere such as a gas or gas mixture
  • a supply for a corresponding gas or gas mixture may be mounted in or on the furnace, so that the furnace chamber containing the porous organometallic framework material can be flooded with the appropriate gas or gas mixture.
  • the porous organometallic framework is heated as necessary to convert the organometallic framework to the corresponding metal oxide. Here- is therefore heated over the complete decomposition temperature of the organometallic framework.
  • complete decomposition temperature is meant the temperature at which the porous organometallic framework material begins to convert into the corresponding metal oxide.
  • organometallic framework material is converted via intermediates to the metal oxide.
  • a carbonate could have been formed prior to formation of the metal oxide.
  • the "complete decomposition temperature” is to be understood as the temperature which is necessary to convert the last intermediate in each case to the metal oxide.
  • the determination of the complete decomposition temperature can be carried out by methods known to the person skilled in the art. For example, this temperature can be determined by thermogravimetry, whereby detection of the formation of the corresponding metal oxide can likewise be carried out by accompanying analysis.
  • the complete decomposition temperature required to produce the corresponding metal oxide from a porous organometallic framework material is typically in the range from 350 ° C. to 1000 ° C. Further preferably, the complete decomposition temperature is in the range from 400 ° C. to 800 ° C. Preferably, the complete decomposition temperature is in the range of 500 ° C. to 750 ° C.
  • the thermally higher-level modification (s) may be obtained from the organometallic framework by applying the appropriate temperature step, or at first the lower-level modification (s) (s) and then in a further step, the conversion can be carried out in the desired modification.
  • the heating of the porous organometallic framework material can take place in a suitable atmosphere.
  • the porous organometallic framework contains at least one at least bidentate organic compound which itself has sufficient oxygen, it is not absolutely necessary to provide an oxygen-providing substance from outside in order to convert the porous organometallic framework into a metal oxide.
  • at least bidentate organic compounds containing oxygen are carboxylic acids, Alcohols, ketones, aldehydes, ethers, esters and phenols.
  • the heating of the porous organometallic framework material could take place in a vacuum. Conveniently, however, the heating is carried out under atmospheric conditions.
  • the heating of the porous organometallic framework could take place in the presence of an inert atmosphere.
  • atmospheres could be formed by gases such as nitrogen, noble gases such as helium or argon, and mixtures thereof. However, this is an exception.
  • heating of the porous organometallic framework material therefore takes place in the presence of an oxidizing atmosphere with an oxygen donating component.
  • an oxidizing atmosphere with an oxygen donating component.
  • oxygen donating component an oxygen donating component.
  • Such oxidizing atmospheres can be obtained by corresponding oxygen-supplying gases or gas mixtures.
  • the simplest and preferred gas mixture is air, which normally contains a sufficiently high proportion of molecular oxygen.
  • the air can be used enriched with additional oxygen.
  • pure oxygen is used as the oxidizing atmosphere.
  • gases or gas mixtures can be used, which are enriched, for example, with molecular oxygen.
  • inert gases would be preferred.
  • suitable gas mixtures can be used to produce an oxidizing atmosphere upon heating of the porous organometallic framework helium, argon, nitrogen, or mixtures thereof, each oxygenated.
  • the porous organometallic framework may be exposed to an oxidizing atmosphere such that the atmosphere is not altered during heating.
  • the gas or gas mixture surrounding the porous organometallic framework material is thus not exchanged, so that the oxygen-supplying constituent of the atmosphere decreases during the heating.
  • the atmosphere during heating relatively constant with respect to its oxygen supplying component by tracking at least this component. It is preferred, however, that the oxygen-providing component be increased during heating. This can serve to control the temperature of the exothermic reaction.
  • the atmosphere is replaced by a gas or gas mixture with a higher proportion of oxygen supplying component. In particular, this can be done by supplying oxygen to the atmosphere after the start of heating, until finally a certain oxygen atmosphere is present. The increase can be gradual or continuous.
  • the porous organometallic framework for the method of producing a metal oxide according to the invention must contain the metal ion corresponding to the metal of the metal oxide.
  • the porous metal organic framework may also contain multiple metal ions independent of the catalyst metal component. In this case, a corresponding metal oxide, which is likewise composed of several metals, is formed.
  • the organometallic framework In the event that multiple metal ions are present in the organometallic framework, at least one of these metal ions must be capable of coordinating the at least one at least bidentate organic compound to yield the corresponding porous organometallic framework. If, in addition, one or more metals are present in ionic form, this or these can likewise be present by co-ordination of the at least one at least bidentate organic compounds or further at least bidentate organic compounds on the structure of the organometallic framework. In addition, however, it is also possible that this is not the case. Finally, in the presence of several metal ions, the ratio of the ions may be in a stoichiometric ratio. In addition, a non-stoichiometric ratio may also be present.
  • doping porous organometallic framework material a so-called doping porous organometallic framework material.
  • doped frameworks are described, for example, in DE-A 10 2005 053 430 of the Applicant.
  • Such doped porous organometallic frameworks are characterized in that the distribution of the doping metal is random.
  • two metal ions of one and the same metal of different oxidation state are considered as two different metal ions.
  • a corresponding metal oxide can be obtained in which the metal is present in different oxidation states.
  • such a metal will be present as metal oxide exclusively in the highest stable oxidation state.
  • the porous organometallic framework material exclusively comprises a metal ion of a metal, in particular an oxidation stage.
  • the loaded porous organometallic framework material is to be converted into a porous metal oxide, particular preference is given to the metals from groups 2, 3, 4 and 13 of the Periodic Table of the Elements.
  • Particularly suitable metals of group 2 of the Periodic Table of the Elements are beryllium, magnesium, calcium, strontium and barium.
  • Particularly suitable metals of the 3rd group of the Periodic Table of the Elements are scandium, yttrium, lanthanum and the lanthanides.
  • Particularly suitable metals of Group 4 of the Periodic Table of the Elements are titanium, zirconium and hafnium.
  • Particularly suitable metals of the 13th group of the Periodic Table of the Elements are aluminum, gallium and indium.
  • metals magnesium, calcium, strontium, barium, zirconium and aluminum are particularly preferred.
  • metal ion or the metal ions from the group of metals consisting of aluminum, magnesium and zirconium.
  • aluminates of the formula M 1 AIO 2 or M 11 Al 2 O 4 can be obtained, wherein M 1 represents a monovalent metal ion and M "is a divalent metal ion.
  • spinels can be obtained.
  • titanates in particular ilmenite (FeTiOs), but also MgTiO 3 , MnTiO 3 , FeTiO 3 , CoTiO 3 , NiTiO 3 , CaTiO 3 , SrTiO 3 , BaTiO 3 , Mg 2 TiO 4 , Zn 2 TiO 4 and Mn 2 TiO 4 .
  • ilmenite FeTiOs
  • MgTiO 3 MnTiO 3
  • FeTiO 3 FeTiO 3
  • CoTiO 3 NiTiO 3
  • CaTiO 3 SrTiO 3
  • BaTiO 3 BaTiO 3
  • zirconium in the organometallic framework material and moreover at least one further metal ion corresponding zirconates can be obtained.
  • step (b) of this process In addition to the scaffold material obtained from the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component, it is also possible to use that scaffold material used in step (b) of this process. As a result, the conversion of the catalyst metal ion and the organometallic porous framework material occurs simultaneously.
  • a step (b 1 ) of the process according to the invention for the preparation of a porous metal oxide loaded with a catalyst metal component a chemical re-conversion to the desired catalyst metal component takes place if appropriate.
  • step (b) of the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component analogously.
  • passivation of the catalyst metal component may optionally take place in a step (c 1 ).
  • step (c) of the process according to the invention for producing a porous organometallic framework material loaded with a catalyst metal component it is preferred that the passivation is carried out at a temperature of at most 100 0 C and also preferably takes place in an air atmosphere.
  • novel metal-organic skeleton material loaded with a catalyst metal component and the metal oxide loaded with a catalyst metal component according to the invention are particularly suitable as catalysts for chemical reactions. In addition, however, these can also be used in gas storage or separation.
  • an object of the present invention relates to the use of an organometallic framework according to the invention as described above or of a metal oxide for gas storage or separation according to the invention as described above.
  • porous metal organic framework material of the invention or metal oxides are used for storage, this is preferably carried out in a temperature range from -200 0 C to +80 0 C. More preferred is a temperature range of -40 0 C to +80 0 C.
  • gas and liquid are used in a simplified manner, but here too gas mixtures and liquid mixtures 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 monoxide and carbon dioxide.
  • dioxide nitrogen oxides, oxygen, sulfur oxides, halogens, halide hydrocarbons, NF 3 , SF 6 , ammonia, boranes, phosphines, hydrogen sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
  • the separation of CO and nitrogen oxides is preferred.
  • the gas is also 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 bed entirely or partially consists of the inventive material.
  • the adsorption phase takes place for the CO 2 / CO-T separation preferably at a CO 2 partial pressure of 0.6 to 3 bar and temperature of at least 20, but at most 70 0 C instead.
  • the total pressure in the relevant adsorber reactor is usually lowered to values between 100 mbar and 1 bar.
  • the framework material or metal oxide 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).
  • the gas is particularly preferably hydrogen or methane, in particular hydrogen.
  • the at least one substance may also be a liquid.
  • a liquid examples of such a liquid are disinfectants, inorganic or organic solvents, fuels - especially gasoline or diesel -, hydraulic, radiator, brake fluid or an oil, especially machine oil.
  • the liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof.
  • the at least one substance may be an odorant.
  • the odorant is a volatile organic or inorganic compound containing at least one of nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine or iodine or an unsaturated or aromatic hydrocarbon or a saturated or unsaturated aldehyde or a ketone is. More preferred elements are nitrogen, oxygen, phosphorus, sulfur, chlorine, bromine; especially preferred are nitrogen, oxygen, phosphorus and sulfur.
  • the odorant is ammonia, hydrogen sulfide, sulfur oxides, nitrogen oxides, ozone, cyclic or acyclic amines, thiols, thioethers and aldehydes, ketones, esters, ethers, acids or alcohols.
  • ammonia hydrogen sulphide
  • organic acids preferably acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, lauric acid, pelargonic acid
  • cyclic or acyclic hydrocarbons which contain nitrogen or sulfur and saturated or unsaturated Aldehydes, such as hexanal, heptanal, octanal, nonanal, decanal, octenal or nonenal, and in particular volatile aldehydes such as butyraldehyde, propionaldehyde, acetaldehyde and formaldehyde, and furthermore 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, camomile oil, eucalyptus oil, rosemary oil, lemon oil, lime oil, orange oil, bergamot oil, muscatel sage oil, Coriander oil, cypress oil, 1, 1-dimethoxy-2-pherylethane, 2,4-dimethyl-4-phenyltetrahydrofuran, dimethyltetrahydrobenzaldehyde, 2,6-dimethyl-7-octene-2-ol, 1, 2-diethoxy-3,7- dimethyl-2,6-octadiene, phenylacetaldehyde, rose oxide, ethyl 2-methylpentanoate, 1- (2,6,6-trimethyl-1,
  • a volatile odorant preferably has a boiling point or boiling point range of less than 300 ° C. More preferably, the odorant is a volatile compound or mixture. Particularly preferably, the odorant has a boiling point or boiling range of less than 250 0 C, more preferably less than 230 0 C, particularly preferably less than 200 0 C.
  • odors which have a high volatility.
  • volatility of the vapor pressure can be used.
  • a volatile odorant preferably has a vapor pressure of more than
  • the odorant is a volatile compound or mixture. More 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 odors have a vapor pressure of more than 0.1 kPa (20 0 C).
  • Another object is the use of a loaded organometallic framework according to the invention or a loaded metal oxide according to the invention as a catalyst for chemical reactions.
  • the chemical reaction is preferably a hydrogenation, dehydrogenation, hydration, dehydration, isomerization, nitrile hydrogenation, aromatization, decarboxylation, oxidation, epoxidation, amination, H 2 C> 2 synthesis, preparation of carbonate, preparation of CI 2 Deacon process, hydrodesulfurization, hydrochlorination, metathesis, alkylation, acylation, ammoxidation, Fischer-Tropsch synthesis, methanol reforming, exhaust gas catalysis (SCR), reduction, especially of nitrogen oxides, carbonylations, CC coupling reaction, CO coupling reaction, CB Coupling reaction, CN coupling reaction, hydroformylation or rearrangement.
  • SCR exhaust gas catalysis
  • the finished product has a Pt content of 0.91%.
  • the elemental analysis (12.7% AI, 43.3% C) and the X-ray diffractogram (XRD) show that the MOF framework was preserved after occupancy / reduction / passivation.
  • TM Transmission Electron Microscopy
  • the finished product has a Pd content of 0.94%.
  • the elemental analysis 13.0% AI, 43.4% C
  • the XRD check show that the MOF framework is preserved.
  • 2-5 nm Pt particles are detected.
  • the N 2 surface (Langmuir) is determined to be 1240 m 2 / g.
  • Al-Terepthalklare MOF is still precalcined for 72 h at 360 0 C in a muffle furnace.
  • the finished product has a Pt content of 0.95%. Elemental analysis (12.6% AI, 45.3% C) and XRD verification confirm that the MOF framework is preserved has remained. In TEM images, 1 to 2 nm Pt particles are detected. The N 2 surface (Langmuir) is determined to be 911 m 2 / g.
  • the surface areas are 736 and 676 m 2 / g.
  • the 17.75 g of a mixed sample of Zr-MOFs are uniformly wetted in a dish with 1.63 g of a 11. 03% Pd (II) nitrate solution, diluted with water to a total of 12.4 ml.
  • the pH of the impregnation solution is less than 1.
  • the loaded with the precursor MOF is first dried at 120 0 C in a vacuum oven within 16 h. Subsequently, the material is heated in a rotary kiln at 100 L / h N 2 to 180 0 C, the gas mixture to 50 L / h N 2 + 50 L / h H 2 and continuously increased during the reduction of H 2 content, until finally a pure H 2 atmosphere is reached. After no more water is detected in the exhaust gas, it is cooled to room temperature under N 2 . Small amounts of air are added for passivation so that the temperature rise is less than 15K. The proportion of air is thus gradually increased to a pure air atmosphere.
  • the finished product has a Pd content of 0.94%. Elemental analysis (29.0% Zr, 36.3% C) suggests that the MOF framework has been conserved.
  • Elemental analysis 29.0% Zr, 36.3% C
  • Pd particles are detected. Occasionally larger Pd agglomerates of more than 5 nm are to be detected.
  • the N 2 surface (Langmuir) is determined to be 584 m 2 / g.
  • the finished product has a Pt content of 0.98%.
  • the elemental analysis (10.8% AI, 43.3% C) and an XRD analysis show that the MOF framework has been preserved.
  • TEM images 1-5 nm Pt particles are detected.
  • the N 2 surface (Langmuir) is determined to be 327 m 2 / g.
  • the dry product has only one N 2 surface area of 21 m 2 / g (Langmuir).
  • the XRD has a completely different structure than the MOF-5 used ( Figure 2). From this it can be concluded that the impregnation resulted in a transformation of the porous MOF-5 structure into another, dense structure.
  • FIG. 2 shows the X-ray diffractogram of the modified material which no longer has a MOF-5 structure.
  • the intensity I (Ln (counts)) is shown as a function of the 2-theta scale (2 ⁇ ).
  • the autoclave are decompressed to ambient pressure, heated to 30 ° C., 80 bar of H 2 are pressed in and the stirrer is started. Switching on the stirrer is the actual start time of the experiment. As soon as the total pressure drops below 60 bar due to the consumption of hydrogen, the original pressure of 80 bar is restored by re-pressurizing hydrogen. The experiment is terminated after 4 hours.
  • the hydrogenation activity of the catalyst tested is determined by the H 2 consumption rate during the first half hour of the experiment.
  • the evaluation was carried out according to the following formula:
  • AKT stands for the hydrogenation activity of the investigated catalyst
  • An (H 2 ) for the amount of hydrogen consumed in the relevant time interval of the experiment (0.5 h), ⁇ t for the relevant time interval (0.5 h) and m Ka t for the catalyst used ,
  • CONV stands for the conversion of nitrobenzene (to aniline)
  • n (H 2 ) for the total H 2 consumption
  • n (C 6 H 5 NO 2 ) for the amount of nirobenzene used. Turnover above 100% indicates hydrogenation of the aromatic nucleus.
  • Example 2 A Pd from Example 2 and an Al-MOF loaded with Pt from Example 5 are tested for hydrogenation activity. Table 1 gives the experimental results for these catalysts. Both prove to be hydrogenating and can convert all nitrobenzene to aniline during the experiment. In direct comparison, the Pd-loaded Al-MOF is more active than the Pt-loaded Al-MOF.

Abstract

La présente invention concerne des procédés de fabrication d'un matériau à réseau organométallique poreux chargé d'un composant métallique catalyseur, qui contient les étapes qui consistent (a) à mettre en contact le matériau en réseau organométallique contenant au moins un composé organique au moins divalent lié par coordination à au moins un ion métallique avec une solution aqueuse qui contient un ion métallique catalyseur qui correspond au composant métallique catalyseur, le ou les ions métalliques et l'ion métallique catalyseur provenant de métaux différents et le ou les ions métalliques étant sélectionnés dans l'ensemble constitué des métaux des groupes 2, 3, 4, 13 du tableau période des éléments et des lanthanides, (b) à convertir chimiquement l'ion métallique catalyseur en le composant métallique catalyseur et (c) à éventuellement passiver le composant métallique catalyseur. L'invention concerne en outre la conversion de matériaux à réseau organométallique poreux chargés en oxydes métalliques poreux, les matériaux poreux ainsi obtenus ainsi que leur utilisation, en particulier dans une réaction chimique catalysée.
EP08736411A 2007-04-24 2008-04-21 Matériaux en réseau organométallique poreux chargés de composants métalliques catalyseur Withdrawn EP2142297A1 (fr)

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