WO2005016849A1 - Oxidic aluminum compounds with metals and fluorine - Google Patents

Oxidic aluminum compounds with metals and fluorine Download PDF

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Publication number
WO2005016849A1
WO2005016849A1 PCT/EP2004/005929 EP2004005929W WO2005016849A1 WO 2005016849 A1 WO2005016849 A1 WO 2005016849A1 EP 2004005929 W EP2004005929 W EP 2004005929W WO 2005016849 A1 WO2005016849 A1 WO 2005016849A1
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aluminum
oxidic
fluorine
metal
modified
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PCT/EP2004/005929
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French (fr)
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Michael Theissen
Michael Hoffmeister
Dietmar Wiese
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Honeywell Specialty Chemicals Seelze Gmbh
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/407—Aluminium oxides or hydroxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/021—After-treatment of oxides or hydroxides
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5031—Alumina
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers

Definitions

  • the invention relates to a process for reacting oxidic aluminum compounds with hexafluorometalic acids to form oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine.
  • the invention further provides the compounds obtained by the process and provides for their use for preparing aqueous coating dispersions and suspensions for catalytically active coatings, as catalysts or supports for catalysts and also as adsorbents.
  • Oxidic aluminum compounds which can be used are, in particular, aluminum oxide and hexafluorometalic acids which can be used are those of elements of transition group IV of the Periodic Table.
  • Oxidic metal compounds comprising aluminum, a further metal and fluorine are already known.
  • a fluorinated hydrocarbon for example trifluoromethane
  • the reaction of mixtures of oxides of titanium, tantalum, niobium, magnesium and zirconium with aluminum oxide is described by way of example.
  • a concrete example discloses the reaction of a mixture of tantalum oxide and a- luminum oxide with trifluoromethane.
  • the above systems can be used as catalysts for cracking and isomerization reactions of hydrocarbons.
  • the compounds can be used as supports for metals of main group 8 of the Periodic Table, for example noble metals.
  • Such supported catalysts can likewise catalyze reactions of the abo- vementioned type.
  • the further metal cation is selected from the group consisting of monovalent metal cations and alkaline earth metal cations.
  • the catalysts can also contain noble metals.
  • the reaction of the oxides with the halogenating agent has to be carried out under anhydrous conditions.
  • the products, too, are very water-sensitive, which makes their handling and use for catalytic purposes more difficult.
  • the invention accordingly provides a process for preparing oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine, characterized in that it comprises the steps (i), (ii) and (iii):
  • step (i) mixing at least one oxidic aluminum compound with at least one hexafluorometalic acid in water, (ii) separating off the insolubles from step (i), (iii) calcining the insolubles separated in step (ii).
  • oxidic aluminum compound or compounds preference is given to using compounds which contain, in addition to aluminum, one or more elements selected from the first to fifth main groups of the Periodic Table, the transition elements and/or the lanthanides.
  • elements are the alkali metals, for e- xample lithium, sodium, potassium; the alkaline earth metals, for example magnesium, calcium; the earth metals, for example boron, gallium.
  • elements of the fourth main group mention may be made by way of example of silicon and germanium, and from the fifth main group, arsenic, antimony and bismuth.
  • transition elements are titanium, chromium, manganese, zirconium, niobium, molybdenum, tungsten.
  • lanthanides are lanthanum and cerium.
  • Abominates can, for example, be described by the formulae M I [Al(OH) 4 ], M ⁇ 2 [Al 2 (OH) 10 ], M ⁇ 3 [Al(OH) 6 ] 2 , M l [M0 2 ], M ⁇ [AlO 2 ] 2 , M ⁇ 3 [AlO 3 ] 2 , M ! 5 [AlO ], where M 1 and M ⁇ are divalent cations selected from the groups of the Periodic Table, as defined above.
  • Aluminosilicates of the zeolite type are, as is known, ones which comprise very porous, three-dimensional anionic networks through which channels extend and in which water molecules and cations can be incorporated. Such cations are preferably cations from the above-defined groups of the Periodic Table. It is also pos- sible for the aluminum in the zeolites to be partly replaced by cations from the groups of the Periodic Table as defined above.
  • Aluminum hydroxide or aluminum oxide hydroxide can also be used advantageously.
  • aluminum oxide hydroxide can be used in the form of - aluminum oxide hydroxide (diaspor), ⁇ -aluminum oxide hydroxide (boehmite) or bauxite.
  • aluminum oxide as an oxidic aluminum compound. It can be in the form of one or more of its known modifica- tions, for example as alpha-, beta-, gamma-, delta-, kappa-, theta- and eta- aluminum oxide.
  • gamma-aluminum oxide ⁇ -Al 2 O
  • oxidic aluminum compound Preference is given to use gamma-aluminum oxide ( ⁇ -Al 2 O ) as oxidic aluminum compound.
  • oxidic aluminum compounds containing one or more of the abovementioned elements it is also possible to use aluminum oxide in admixture with suitable compounds of these elements.
  • the oxides are preferably used as suitable compounds of these elements.
  • mixtures of titanium dioxide and aluminum oxide, silicon dioxide and aluminum oxide, lanthanum oxide and aluminum oxide, cerium oxide and aluminum oxide can be reacted with the hexafluorometalic acid or acids in the process.
  • hexafluorometalic acids are likewise known from the prior art. They are preferably prepared from metal fluorides by reaction with hydrogen fluoride.
  • hexafluorozirconic acid (H 2 ZrF 6 ) can be obtained by reaction of zirconium tetrafluoride with hydrofluoric acid (Gmelins Handbuch der Anorgani- schen Chemie, 1958 edition, p.278 ff).
  • the reaction of titanium tetrafluoride with hydrogen fluoride to form hexafluorotitanic acid (H TiF 6 ) is likewise known (Gmelins Handbuch der Anorganischen Chemie, 8 th edition 1951, p.288).
  • He- xafluorohafhic acid may also be mentioned as a further acid of the elements of transition group IN of the Periodic Table.
  • hexafluorovanadic acid HNF 6
  • hexafluorotantalic and hexafluoroni- obic acids for example HTaF 6 and H ⁇ bF 6
  • hexafluoroiridic and hexafluororodic acid for example HIrF 6 and HRhF 6
  • hexafluoroargentic acid H 3 AgF 6
  • hexafluo- roauric acid H 3 AuF 6
  • hexafluorocobaltic acid H 2 CoF 6
  • hexafluoromanganic acid for example H 2 MnF 6 ).
  • hexafluoro- lanthanic acid H 3 LaF 6 .
  • hexafluorometalic acids additional examples include those of elements of main group III of the Periodic Table, for example hexafluoroaluminic acid
  • H 3 A1F 6 hexafluorogallic acid (H 3 GaF 6 ) and hexafluoroindic acid (H 3 InF 6 ), the elements of main group IN, e.g. hexafluorogermanic acid (H GeF 6 ) and hexafluo- rosilicic acid (H 2 SiF 6 ), or those of main group N, e.g. hexafluoroantimonic acid (HSbF 6 ) and hexafluoroarsenic acid (HAsF ).
  • main group IN e.g. hexafluorogermanic acid (H GeF 6 ) and hexafluo- rosilicic acid (H 2 SiF 6
  • main group N e.g. hexafluoroantimonic acid (HSbF 6 ) and hexafluoroarsenic acid (HAsF ).
  • the compounds are frequently not stable in pure form and can therefore not be isolated or stored in pure form.
  • they can in this case usually be used in the form of aqueous solutions in which they can have the stability necessary for the process.
  • the said acids can also be present in aqueous solution in the form of their oxonium salts.
  • hexafluorozirconic acid forms stable solutions with water.
  • hexafluorometalic acids of the elements of transition group IN of the Periodic Table e.g., hexafluorotitanic acid (H 2 TiF 6 ), hexafluorozirconic acid (H 2 ZrF 6 ) and hexafluorohafnic acid.
  • hexafluorotitanic acid H 2 TiF 6
  • he- xafluorozirconic acid H 2 ZrF 6
  • the oxidic aluminum compound and the hexafluorometalic acid are preferably mixed in a ratio of from 1 : 0.01 to 1 : 10, based on the weight. Particular preference is given to a weight ratio of from 1 : 0.5 to 1 : 5.
  • the reaction temperature does not have to meet any particular requirements. It is usually sufficient to mix the components at room temperature in step (i).
  • the insolubles present in the product are separated off from the mixture.
  • the separation can be carried out by customary methods such as sedimentation, filtration and pressing on a filter, and/or other separation techniques known by those skilled in the art.
  • the separation can be carried out using the customary apparatuses such as thickeners, centrifuges and filters, and/or other equipment known in the art.
  • the product is preferably freed of adhering traces of acid by washing one or more times with water.
  • the product separated off in step (ii) is preferably dried to remove most of the water still present, and a heat treatment step can also follow.
  • the drying tempe- rature and, if applicable, the heat treatment temperature are preferably in the range from about 50 to about 300°C.
  • step (iii) The product which has been separated off in step (ii) is then calcined in step (iii).
  • the temperature used here is preferably from about 300 to about 1300°C. In particular, more preferablty, a calcination temperature of from about 600 to about 1000°C is used. During the calcination, the formation of the oxidic aluminum compound modified with at least one further metal and fluorine is completed.
  • the product is generally obtained in the form of coarse lumps. It is then preferably milled before being used further.
  • composition of the oxidic compounds modified with at least one further metal other than aluminum and fluorine can be controlled via the type of starting mate- rials used, the concentration of hexafluorometalic acid and also via the calcination temperature. In this way, physical properties which are of importance for the envisaged use can be varied.
  • an increasing calcination temperature preferably above 600°C, can further reduce the content of incorporated fluorine.
  • the specific surface area of the product can be influence by means of the calcination temperature.
  • the specific surface area can be reduced further at higher temperature.
  • Y hile for example, the specific surface area at a calcination temperature of up to 600°C can still be about 10% above that of the aluminum oxide used, it can be reduced to about 50% of its original value by calcination at higher temperature, for instance at about 800°C.
  • the specific surface area here is measured by the BET method in accordance with DIN 66 131. This variability of the method enables the metal and fluorine contents of the product to be optimized and matched to the envisaged use.
  • the modified oxidic aluminum compounds prepared by the process preferably have an aluminum content of from about 30 to about 53% by weight, a content of the further metal or metals of from about 0.01 to about 20% by weight, a fluorine content of from about 0.01 to about 15% by weight and an oxygen content of from about 20 to about 47% by weight, with the sum of all elements present in the product being about 100% by weight.
  • the content of the elements concerned is determined by customary methods, i.e. wet chemically and/or spectroscopically.
  • the invention therefore also provides oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine which are characterized in that they can be prepared by a process as defined in any of Claims 1 to 7.
  • the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine are preferably used for processes in which adsorption and desorption are important.
  • they can be used as adsorbents, catalysts or catalyst supports.
  • adsorbents When used as adsorbents, they are preferably used for chromatographic methods, for example as stationary phase for thin layer, thick layer, column or gas chroma- tography.
  • suitable materials such as glass are coated with the said compounds by customary methods or else columns filled with the said compounds.
  • the products can are employed preferably either in powder form or in the form of coarse pieces. However, they are most preferably used as shaped bodies.
  • Such shaped bodies can, for example, be built up from customary packing elements or supports to which the modified oxidic aluminum compound is applied.
  • Such supports are, for example, Raschig rings, saddle bodies, Pall rings, wire spirals or wire mesh rings made of various materials which are suitable for coating with the active component.
  • Ceramic supports for example in the form of honey- combs, can also be used advantageously.
  • packing elements as supports are also referred to as catalyst monoliths.
  • the said modified oxidic aluminum compounds are suspended or dispersed in water.
  • Customary binders and auxiliaries for e- xample cellulose ethers, can be added during this procedure.
  • the resulting suspensions or dispersions are also referred to as "washcoats".
  • the said washcoats can be used to coat the shaped bodies by known methods.
  • the coated shaped bodies are subsequently dried and then calcined.
  • the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine are particularly suitable for preparing such washcoats, since the said dispersions or suspensions then contain no constituents present in heterogeneous form which could settle out from the suspension or dispersion.
  • shaping can also be carried out by extrusion in customary extruders. If binders and/or auxiliaries are required, extrusion is advantageously preceded by a mixing or kneading process. Another calcination step may be carried out after extrusion if appropriate. The extrudates obtained can also be comminuted if necessary.
  • suitable shaped bodies can also be produced by other known methods, for example tabletting or agglomeration.
  • metals such as noble metals, e.g. platinum or palladium, can be applied.
  • the noble metals can be ap- plied to the catalyst in the form of suitable noble metal compounds, for example in the form of water-soluble salts, before, during or after the consolidating shaping step.
  • Shaped bodies which have been coated with a washcoat prepared in such a way can, for example, be used for the catalytic purification of waste gases which are passed over the shaped bodies.
  • the purification step preferably comprises an oxidation of the waste gases.
  • waste gases preferably contain carbon monoxide and/or hydrocarbons.
  • these compounds can then be oxidized to carbon di- oxide or carbon dioxide and water over the catalytically shaped body.
  • the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine can advantageously be used for the oxidation of automobile exhaust gases.
  • the said oxidic aluminum compounds are preferably used for preparing aqueous coating dispersions or suspensions for catalytically active coatings.
  • the said modified oxidic aluminum compounds are also preferably used for the catalytic oxidation of waste gases and are in this case preferably applied to shaped bodies.
  • the invention is illustrated by the following examples.
  • the BET surface area of the dried samples increases with increasing zirconium content. Calcination at 450°C results in a slight decrea- se in the fluorine and zirconium contents, while the BET surface area drops. During calcination at 850°C, the BET surface area decreases further; the higher the zirconium content the higher the decrease. The fluorine content also drops sharply, while the zirconium content remains virtually constant.
  • Example 4 Preparation of oxidic aluminum compounds modified with zirconium and fluorine by reaction of aluminum oxide with hexafluorozirconic acid
  • the suspension formed was stirred for 30 minutes, subsequently filtered off with suction and the resulting solid was washed with water. The solid was then dried and calcined at different temperatures and for different times. The zirconium and fluorine contents and the BET surface area were then determined by customary methods. The values found are listed in Table 2.
  • the calcination temperature and time may effect the zirconium content, the fluorine content, and the BET surface area.
  • the BET surface area as can be seen in the table drops at elevated temperatures and prolonged calcination times because of sintering effects.

Abstract

Process for preparing oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine, characterized in that it comprises the steps (i), (ii) and (iii): (i) mixing at least one oxidic aluminum compound with at least one hexafluorometalic acid in water, (ii) separating off the insolubles from step (i), (iii) calcining the insolubles separated in step (ii).

Description

Oxidic Aluminum compounds modified with Metals and Fluorine
The invention relates to a process for reacting oxidic aluminum compounds with hexafluorometalic acids to form oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine. The invention further provides the compounds obtained by the process and provides for their use for preparing aqueous coating dispersions and suspensions for catalytically active coatings, as catalysts or supports for catalysts and also as adsorbents. Oxidic aluminum compounds which can be used are, in particular, aluminum oxide and hexafluorometalic acids which can be used are those of elements of transition group IV of the Periodic Table.
Oxidic metal compounds comprising aluminum, a further metal and fluorine are already known.
US-A 4,402,924, hereby incorporated by reference, discloses a process by means of which compounds of this type are said to be obtainable by reaction of a mixture of a metal oxide and aluminum oxide with a fluorinated hydrocarbon, for example trifluoromethane, at a temperature of from 300 to 800°C and a pressure of from 0.001 to 1 at. The reaction of mixtures of oxides of titanium, tantalum, niobium, magnesium and zirconium with aluminum oxide is described by way of example. A concrete example discloses the reaction of a mixture of tantalum oxide and a- luminum oxide with trifluoromethane.
However, only aluminum fluoride together with tantalum oxyfluoride and un- reacted aluminum oxide and tantalum oxide were able to be found in the reaction product by means of X-ray diffraction. It is therefore questionable whether compounds made up of aluminum, the further metal, fluorine and oxygen are actually formed in the process mentioned. It is more likely that only heterogeneous mixtu- res of aluminum fluoride, metal oxyfluoride and the unreacted oxides are formed. Furthermore, working with fluorinated hydrocarbons, which can be toxic and damaging to the environment, requires increased safety measures.
It is also known from this patent that the above systems can be used as catalysts for cracking and isomerization reactions of hydrocarbons. The compounds can be used as supports for metals of main group 8 of the Periodic Table, for example noble metals. Such supported catalysts can likewise catalyze reactions of the abo- vementioned type.
Furthermore, it is known from US-A 5,962,760, also incorporated by reference, that catalysts composed of a heat-resistant inorganic metal oxide, the reaction product of a metal halide bearing hydroxyl groups of the said inorganic heat- resistant metal oxides and a further metal cation can.be used for the alkylation of benzene. As heat-resistant inorganic oxides, mention is made of, inter alia, the oxides of aluminum, zirconium, titanium, chromium, silicon and boron, with the oxides also being able to be present as mixtures. As halogenating agent, it is possible to use the fluoride, chloride or bromide of aluminum or zirconium. The further metal cation is selected from the group consisting of monovalent metal cations and alkaline earth metal cations. The catalysts can also contain noble metals. The reaction of the oxides with the halogenating agent has to be carried out under anhydrous conditions. The products, too, are very water-sensitive, which makes their handling and use for catalytic purposes more difficult.
It is an object of the present invention to provide a process for preparing oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine, preferably without the use of fluorinated hydrocarbons and gives homogeneous products which are insensitive to water.
This object has been able to be achieved by reacting oxidic aluminum compounds with hexafluorometalic acids in water. The invention accordingly provides a process for preparing oxidic aluminum compounds which are modified with at least one further metal other than aluminum and fluorine, characterized in that it comprises the steps (i), (ii) and (iii):
(i) mixing at least one oxidic aluminum compound with at least one hexafluorometalic acid in water, (ii) separating off the insolubles from step (i), (iii) calcining the insolubles separated in step (ii).
As oxidic aluminum compound or compounds, preference is given to using compounds which contain, in addition to aluminum, one or more elements selected from the first to fifth main groups of the Periodic Table, the transition elements and/or the lanthanides. Examples of such elements are the alkali metals, for e- xample lithium, sodium, potassium; the alkaline earth metals, for example magnesium, calcium; the earth metals, for example boron, gallium. As elements of the fourth main group, mention may be made by way of example of silicon and germanium, and from the fifth main group, arsenic, antimony and bismuth. Examples of transition elements are titanium, chromium, manganese, zirconium, niobium, molybdenum, tungsten. Examples of lanthanides are lanthanum and cerium.
Further preference is given to using oxidic aluminum compounds which are known to be able to be used as catalyst precursors or catalysts; cf. "Marshall Sittig Handbook of catalyst manufacture", published 1978, ISBN 0-8155-0686-4, which is incorporated by reference.
Examples of such compounds are aluminates, mixed aluminum oxides, in particular aluminosilicates of the zeolite type, aluminum hydroxides and aluminum oxides. Abominates can, for example, be described by the formulae MI[Al(OH)4], Mπ 2[Al2(OH)10], Mπ 3[Al(OH)6]2,
Figure imgf000005_0001
Ml[M02], Mπ[AlO2]2, Mπ 3[AlO3]2, M! 5[AlO ], where M1 and Mπ are divalent cations selected from the groups of the Periodic Table, as defined above.
Aluminosilicates of the zeolite type are, as is known, ones which comprise very porous, three-dimensional anionic networks through which channels extend and in which water molecules and cations can be incorporated. Such cations are preferably cations from the above-defined groups of the Periodic Table. It is also pos- sible for the aluminum in the zeolites to be partly replaced by cations from the groups of the Periodic Table as defined above.
Aluminum hydroxide or aluminum oxide hydroxide can also be used advantageously. For example, aluminum oxide hydroxide can be used in the form of - aluminum oxide hydroxide (diaspor), γ-aluminum oxide hydroxide (boehmite) or bauxite.
However, particular preference is given to using aluminum oxide as an oxidic aluminum compound. It can be in the form of one or more of its known modifica- tions, for example as alpha-, beta-, gamma-, delta-, kappa-, theta- and eta- aluminum oxide.
Preference is given to use gamma-aluminum oxide (γ-Al2O ) as oxidic aluminum compound.
However, instead of oxidic aluminum compounds containing one or more of the abovementioned elements, it is also possible to use aluminum oxide in admixture with suitable compounds of these elements. The oxides are preferably used as suitable compounds of these elements. For example, mixtures of titanium dioxide and aluminum oxide, silicon dioxide and aluminum oxide, lanthanum oxide and aluminum oxide, cerium oxide and aluminum oxide can be reacted with the hexafluorometalic acid or acids in the process.
Several examples of hexafluorometalic acids are likewise known from the prior art. They are preferably prepared from metal fluorides by reaction with hydrogen fluoride.
For example, hexafluorozirconic acid (H2ZrF6) can be obtained by reaction of zirconium tetrafluoride with hydrofluoric acid (Gmelins Handbuch der Anorgani- schen Chemie, 1958 edition, p.278 ff). The reaction of titanium tetrafluoride with hydrogen fluoride to form hexafluorotitanic acid (H TiF6) is likewise known (Gmelins Handbuch der Anorganischen Chemie, 8th edition 1951, p.288). He- xafluorohafhic acid may also be mentioned as a further acid of the elements of transition group IN of the Periodic Table.
Other suitable hexafluorometalic acids are those of the further transition elements. As examples from the other transition groups of the Periodic Table, mention may be made of hexafluorovanadic acid (HNF6), hexafluorotantalic and hexafluoroni- obic acids (for example HTaF6 and HΝbF6), hexafluoroiridic and hexafluororodic acid (for example HIrF6 and HRhF6), hexafluoroargentic acid (H3AgF6), hexafluo- roauric acid (H3AuF6), hexafluorocobaltic acid (H2CoF6), hexafluoromanganic acid (for example H2MnF6).
As an example from the lanthanide group, mention may be made of hexafluoro- lanthanic acid (H3LaF6).
As further hexafluorometalic acids, additional examples include those of elements of main group III of the Periodic Table, for example hexafluoroaluminic acid
(H3A1F6), hexafluorogallic acid (H3GaF6) and hexafluoroindic acid (H3InF6), the elements of main group IN, e.g. hexafluorogermanic acid (H GeF6) and hexafluo- rosilicic acid (H2SiF6), or those of main group N, e.g. hexafluoroantimonic acid (HSbF6) and hexafluoroarsenic acid (HAsF ).
It is not necessary to use the hexafluorometalic acids in pure form in the process. Moreover, the compounds are frequently not stable in pure form and can therefore not be isolated or stored in pure form. However, they can in this case usually be used in the form of aqueous solutions in which they can have the stability necessary for the process. The said acids can also be present in aqueous solution in the form of their oxonium salts.
For example, hexafluorozirconic acid (H ZrF6) forms stable solutions with water.
Multiple metalic acids can also be used as mixtures in the process.
Preference is given to using hexafluorometalic acids of the elements of transition group IN of the Periodic Table, e.g., hexafluorotitanic acid (H2TiF6), hexafluorozirconic acid (H2ZrF6) and hexafluorohafnic acid.
Particular preference is given to using hexafluorotitanic acid (H2TiF6) and he- xafluorozirconic acid (H2ZrF6).
Very particular preference is given to using hexafluorozirconic acid (H2ZrF6).
Particular preference is also given to processes in which aluminum oxide as oxidic aluminum compound is reacted with hexafluorotitanic acid and/or hexafluorozirconic acid as the hexafluorometalic acid or acids to form aluminum oxide modified with titanium and/or zirconium and fluorine.
Very particular preference is given to a process in which aluminum oxide as oxi- die aluminum compound is reacted with hexafluorozirconic acid as hexafluorometalic acid to form aluminum oxide modified with zirconium and fluorine. The process for preparing the modified oxidic aluminum compounds can be carried out as follows. For this purpose, an aqueous suspension of the oxidic aluminum compound is stirred with one or more hexafluorometalic acids in step (i). The acid can also be used as an aqueous solution.
In the novel process, the oxidic aluminum compound and the hexafluorometalic acid are preferably mixed in a ratio of from 1 : 0.01 to 1 : 10, based on the weight. Particular preference is given to a weight ratio of from 1 : 0.5 to 1 : 5.
The reaction temperature does not have to meet any particular requirements. It is usually sufficient to mix the components at room temperature in step (i).
Reaction of the oxidic aluminum compound with the hexafluorometalic acid oc- curs even during mixing, with the oxidic aluminum compound modified with at least one further metal and fluorine beginning to form. The commencing reaction then becomes noticeable by evolution of heat, with the mixture becoming warm. Warming generally occurs to a greater extent, the greater the proportion of hexafluorometalic acid added.
After mixing has been completed and the reaction has ended, the insolubles present in the product are separated off from the mixture. The separation can be carried out by customary methods such as sedimentation, filtration and pressing on a filter, and/or other separation techniques known by those skilled in the art. The separation can be carried out using the customary apparatuses such as thickeners, centrifuges and filters, and/or other equipment known in the art. The product is preferably freed of adhering traces of acid by washing one or more times with water.
The product separated off in step (ii) is preferably dried to remove most of the water still present, and a heat treatment step can also follow. The drying tempe- rature and, if applicable, the heat treatment temperature are preferably in the range from about 50 to about 300°C.
The product which has been separated off in step (ii) is then calcined in step (iii). The temperature used here is preferably from about 300 to about 1300°C. In particular, more preferablty, a calcination temperature of from about 600 to about 1000°C is used. During the calcination, the formation of the oxidic aluminum compound modified with at least one further metal and fluorine is completed.
After the calcination, the product is generally obtained in the form of coarse lumps. It is then preferably milled before being used further.
The composition of the oxidic compounds modified with at least one further metal other than aluminum and fluorine can be controlled via the type of starting mate- rials used, the concentration of hexafluorometalic acid and also via the calcination temperature. In this way, physical properties which are of importance for the envisaged use can be varied.
For example, an increasing calcination temperature, preferably above 600°C, can further reduce the content of incorporated fluorine.
It is also possible to influence the specific surface area of the product by means of the calcination temperature. In the calcination of the preferred modified oxidic aluminum compound, the specific surface area can be reduced further at higher temperature. Y hile, for example, the specific surface area at a calcination temperature of up to 600°C can still be about 10% above that of the aluminum oxide used, it can be reduced to about 50% of its original value by calcination at higher temperature, for instance at about 800°C. The specific surface area here is measured by the BET method in accordance with DIN 66 131. This variability of the method enables the metal and fluorine contents of the product to be optimized and matched to the envisaged use.
The modified oxidic aluminum compounds prepared by the process preferably have an aluminum content of from about 30 to about 53% by weight, a content of the further metal or metals of from about 0.01 to about 20% by weight, a fluorine content of from about 0.01 to about 15% by weight and an oxygen content of from about 20 to about 47% by weight, with the sum of all elements present in the product being about 100% by weight.
The content of the elements concerned is determined by customary methods, i.e. wet chemically and/or spectroscopically.
The invention therefore also provides oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine which are characterized in that they can be prepared by a process as defined in any of Claims 1 to 7.
The oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine are preferably used for processes in which adsorption and desorption are important.
Thus, for example, they can be used as adsorbents, catalysts or catalyst supports.
When used as adsorbents, they are preferably used for chromatographic methods, for example as stationary phase for thin layer, thick layer, column or gas chroma- tography. For this purpose, suitable materials such as glass are coated with the said compounds by customary methods or else columns filled with the said compounds. For use as catalyst supports or as catalysts, the products can are employed preferably either in powder form or in the form of coarse pieces. However, they are most preferably used as shaped bodies.
Such shaped bodies can, for example, be built up from customary packing elements or supports to which the modified oxidic aluminum compound is applied. Such supports are, for example, Raschig rings, saddle bodies, Pall rings, wire spirals or wire mesh rings made of various materials which are suitable for coating with the active component. Ceramic supports, for example in the form of honey- combs, can also be used advantageously. Such packing elements as supports are also referred to as catalyst monoliths.
To produce these shaped bodies, the said modified oxidic aluminum compounds are suspended or dispersed in water. Customary binders and auxiliaries, for e- xample cellulose ethers, can be added during this procedure. The resulting suspensions or dispersions are also referred to as "washcoats".
The said washcoats can be used to coat the shaped bodies by known methods. The coated shaped bodies are subsequently dried and then calcined.
Owing to their homogeneous structure, the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine are particularly suitable for preparing such washcoats, since the said dispersions or suspensions then contain no constituents present in heterogeneous form which could settle out from the suspension or dispersion. The suspension or dispersion, too, therefore remains homogeneous, which is very preferable for use as a coating which is to have a uniform catalytic activity.
As consolidating shaping processes, it is possible to use further methods as are generally customary in the field of catalysts. For example, shaping can also be carried out by extrusion in customary extruders. If binders and/or auxiliaries are required, extrusion is advantageously preceded by a mixing or kneading process. Another calcination step may be carried out after extrusion if appropriate. The extrudates obtained can also be comminuted if necessary. However, suitable shaped bodies can also be produced by other known methods, for example tabletting or agglomeration.
It is also possible to apply further components which are catalytically active to the said modified oxidic aluminum compounds. For example, metals such as noble metals, e.g. platinum or palladium, can be applied. The noble metals can be ap- plied to the catalyst in the form of suitable noble metal compounds, for example in the form of water-soluble salts, before, during or after the consolidating shaping step.
However, such components are preferably added to the washcoat. Shaped bodies which have been coated with a washcoat prepared in such a way can, for example, be used for the catalytic purification of waste gases which are passed over the shaped bodies. The purification step preferably comprises an oxidation of the waste gases. Such waste gases preferably contain carbon monoxide and/or hydrocarbons. In the purification, these compounds can then be oxidized to carbon di- oxide or carbon dioxide and water over the catalytically shaped body.
The oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine can advantageously be used for the oxidation of automobile exhaust gases.
In this case, the said oxidic aluminum compounds are preferably used for preparing aqueous coating dispersions or suspensions for catalytically active coatings.
In particular, the said modified oxidic aluminum compounds are also preferably used for the catalytic oxidation of waste gases and are in this case preferably applied to shaped bodies. The invention is illustrated by the following examples.
Examples 1, 2 and 3: Preparation of oxidic aluminum compounds modified with zirconium and fluorine by reaction of aluminum oxide with hexafluorozirconic acid
100 g of aluminum oxide were suspended in 150 g of water. While stirring, about 90 ml of water containing 51.75 g of hexafluorozirconic acid (Example 1), 207 g of hexafluorozirconic acid (Example 2) or 414 g of hexafluorozirconic acid (E- xample 3) were added thereto. The suspensions formed were in each case stirred for 30 minutes, subsequently filtered off with suction and the resulting solid was washed with water. The solid was then dried and calcined. The zirconium and fluorine contents and the BET surface area were then determined by customary methods. The values found are listed in Table 1, in which aluminum oxide is also listed as a blank for comparison.
As can be seen from the table, the BET surface area of the dried samples increases with increasing zirconium content. Calcination at 450°C results in a slight decrea- se in the fluorine and zirconium contents, while the BET surface area drops. During calcination at 850°C, the BET surface area decreases further; the higher the zirconium content the higher the decrease. The fluorine content also drops sharply, while the zirconium content remains virtually constant.
Table 1 :
Comparison Example 1 Example 2 Example 3
Values after drying at 90°C:
Yield [% by weight] 95.70 101.80 104.60 98.30
Zirconium content [% by 0.004 2.2 4.5 4.2 weight]
Fluorine content 0.09 3.03 3.51 3.21
[°/o by weight]
BET surface area [m2/g] 92.7 104.77 114.29 111.81
Values after calcinations at 45 0°C for 5 h:
Zirconium content [% by 2.2 3.5 3.80 weight]
Fluorine content 0.28 1.88 2.46 2.75
[% by weight]
BET surface area 92.47 94.00 93.34 96.78
[m2/g]
Values after calcinations at 850°C for 5 h:
Zirconium content not determined not determined not determined 4.2
[% by weight]
Fluorine content not determined not determined not determined 0.56
[% by weight]
BET surface area 87.54 73.21 50.89 48.05
[m2/g]
Example 4: Preparation of oxidic aluminum compounds modified with zirconium and fluorine by reaction of aluminum oxide with hexafluorozirconic acid
100 g of aluminum oxide were suspended in 150 g of water. While stirring, about 90 ml of water containing 51.75 g of hexafluorozirconic acid were added thereto.
The suspension formed was stirred for 30 minutes, subsequently filtered off with suction and the resulting solid was washed with water. The solid was then dried and calcined at different temperatures and for different times. The zirconium and fluorine contents and the BET surface area were then determined by customary methods. The values found are listed in Table 2.
Table 2:
Figure imgf000015_0001
As shown above, the calcination temperature and time may effect the zirconium content, the fluorine content, and the BET surface area.
The BET surface area as can be seen in the table drops at elevated temperatures and prolonged calcination times because of sintering effects.
The examples of the components that can be used with the invention are not ex- haustive and should not be used for limiting the scope of the claims.

Claims

Claims
1. Process for preparing an oxidic aluminum compound which is modified with at least one further metal other than aluminum and fluorine, characterized in that it comprises the steps (i), (ii) and (iii):
(i) mixing at least one oxidic aluminum compound with at least one hexafluorometalic acid in water, (ii) separating off the insolubles from step (i), (iii) calcining the insolubles separated in step (ii).
2. Process according to Claim 1, characterized in that the oxidic aluminum compound or compounds is aluminum oxide.
3. Process according to Claim 1 or 2, characterized in that the metal of the hexafluorometalic acid or acids is selected from transition group IN of the Periodic Table.
4. Process according to any of Claims 1 to 3, characterized in that the mixing in step (i) is carried out in the presence of one or more oxygen-containing compounds of elements selected from the group consisting of the elements of main groups 1 to 5 of the Periodic Table, the transition elements and the lanthanides.
5. Process according to any of Claims 1 to 4, characterized in that the oxidic aluminum compound or compounds is mixed with the hexafluorometalic acid or acids in a weight ratio of from about 1:0.01 to about 1:10.
6. Process according to any of Claims 1 to 4, characterized in that the calci- nation in step (iii) is carried out at a temperature of from about 300 to a- bout 1300°C.
7. Process according to any of Claims 1 to 6, characterized in that the aluminum content of the oxidic aluminum compound modified with at least one further metal other than aluminum and fluorine is from about 30 to about 53% by weight, the content of the metal other than aluminum is from a- bout 0.01 to about 20% by weight, the fluorine content is from about 0.01 to about 15% by weight and the oxygen content is from about 20 to about 47% by weight.
8. Oxidic aluminum compound modified with at least one further metal other than aluminum and fluorine, obtainable according to any of Claims 1 to 7.
9. Use of the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine according to Claim 8 as adsor- bents, catalyst supports or catalysts.
10. Use the oxidic aluminum compound modified with at least one further metal other than aluminum and fluorine according to Claim 8 for aqueous coating dispersions or suspensions for catalytically active coatings.
11. Use of the oxidic aluminum compounds modified with at least one further metal other than aluminum and fluorine according to Claim 8 for the catalytic oxidation of waste gases.
12. Use according to any of claims 9 to 11 including one or more further catalytically active component(s).
13. Use according to claim 12 wherein the catalytically active component is a noble metal.
14. Use according to claim 13 wherein the noble metal is platinum and/or palladium.
15. Catalytically active composition, containing the oxidic aluminum com- pound as defined in claim 8 and one or more further catalytically active component(s).
16. Composition according to claim 15 wherein the catalytically active component is a noble metal.
17. Composition according to claim 16 wherein the noble metal is platinum and/or palladium.
18. Process according to any of claims 1 to 7 further comprising a step whe- rein one or more catalytically active component(s) are applied to the modified oxidic aluminum compound.
19. Process according to claim 18 wherein the catalytically active component is a noble metal.
20. Process according to claim 19 wherein the noble metal is platinum and/or palladium.
PCT/EP2004/005929 2003-08-13 2004-06-02 Oxidic aluminum compounds with metals and fluorine WO2005016849A1 (en)

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